WO2018236182A1 - Compound and organic electroluminescent device comprising same - Google Patents

Compound and organic electroluminescent device comprising same Download PDF

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WO2018236182A1
WO2018236182A1 PCT/KR2018/007083 KR2018007083W WO2018236182A1 WO 2018236182 A1 WO2018236182 A1 WO 2018236182A1 KR 2018007083 W KR2018007083 W KR 2018007083W WO 2018236182 A1 WO2018236182 A1 WO 2018236182A1
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group
substituted
compound
unsubstituted
solvent
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PCT/KR2018/007083
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French (fr)
Korean (ko)
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김영석
김민준
권혁준
김동희
김공겸
이민우
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주식회사 엘지화학
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Priority to CN201880011174.4A priority Critical patent/CN110291066B/en
Publication of WO2018236182A1 publication Critical patent/WO2018236182A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to a compound and an organic electroluminescent device including the same.
  • An electroluminescent device is one type of self-luminous display device, and has advantages of wide viewing angle, excellent contrast, and high response speed.
  • the organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light emitting device having such a structure, electrons and holes injected from the two electrodes couple to each other in the organic thin film and form a pair, which then extinguishes and emits light.
  • the organic thin film may be composed of a single layer or a multilayer, if necessary.
  • the material of the organic thin film may have a light emitting function as needed.
  • a compound capable of forming a light emitting layer by itself may be used, or a compound capable of serving as a host or a dopant of a host-dopant light emitting layer may be used.
  • a compound capable of performing a role such as hole injection, hole transport, electron blocking, hole blocking, electron transport or electron injection may be used.
  • the present invention provides a compound and an organic electroluminescent device including the same.
  • the present application provides a compound represented by the following general formula (1).
  • Ar 1 is a divalent substituted or unsubstituted heterocyclic group containing N,
  • X is O or S
  • L 1 and L 2 are the same or different from each other and are each independently a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted divalent heterocyclic group,
  • R 1 to R 4 are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, A substituted or unsubstituted heterocyclic group,
  • n is an integer of 0 to 4, and when n is 2 or more, R1 is the same or different from each other,
  • n is an integer of 0 to 6, and when m is 2 or more, R2 is the same or different,
  • o is an integer of 0 to 3, and when o is 2 or more, R3 is the same or different from each other,
  • p is an integer of 0 to 4, and when p is 2 or more, R4 is the same or different from each other,
  • the present application also includes a first electrode; A second electrode facing the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the above-described compound.
  • the compound according to one embodiment of the present application is used in an organic electroluminescent device to lower the driving voltage of the organic electroluminescent device, to improve the light efficiency, and to improve the lifetime of the device by the thermal stability of the compound.
  • Fig. 1 shows an example of an organic electroluminescent device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially laminated.
  • Fig. 2 is a cross-sectional view showing the structure of a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, an electron blocking layer 7, a light emitting layer 3, a hole blocking layer 8, 9) and a cathode 4 are sequentially laminated on a substrate 1.
  • FIG. 3 is 1H-NMR data of formula (A) according to one embodiment of the present invention.
  • the present invention provides a compound represented by the above formula (1).
  • the compound represented by the general formula (1) according to the present invention is a compound in which two ring heterocyclic groups including N are bonded to benzocarbazole, so that the electron injecting and transporting ability becomes smooth and the dibenzofurane group and dibenzothiophene group are simultaneously introduced Steric hindrance is generated to interfere with the formation of an intermolecular aggregate, so that driving voltage reduction, efficiency and lifetime characteristics are improved in manufacturing an organic light emitting device.
  • substituted means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the substituted position is not limited as long as the substituent is a substitutable position, , Two or more substituents may be the same as or different from each other.
  • substituted or unsubstituted A halogen group; Cyano; An alkyl group; A cycloalkyl group; An alkenyl group; An alkoxy group; A substituted or unsubstituted phosphine oxide group; An aryl group; And a heterocyclic group, or that at least two of the substituents exemplified in the above exemplified substituents are substituted with a connected substituent, or have no substituent.
  • a substituent to which at least two substituents are connected may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.
  • examples of the halogen group include fluorine, chlorine, bromine or iodine.
  • the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50.
  • Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec- N-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-hexyl, Cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methyl
  • the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, But are not limited to, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert- butylcyclohexyl, cycloheptyl, Do not.
  • the alkoxy group may be linear, branched or cyclic.
  • the number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n Butyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like. But is not limited thereto.
  • the phosphine oxide group specifically includes a diphenylphosphine oxide group, dinaphthylphosphine oxide, and the like, but is not limited thereto.
  • the aryl group is a monocyclic aryl group
  • the number of carbon atoms is not particularly limited, but is preferably 6 to 25 carbon atoms.
  • Specific examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group, and the like, but are not limited thereto.
  • the aryl group is a polycyclic aryl group
  • the number of carbon atoms is not particularly limited. And preferably has 10 to 24 carbon atoms.
  • Specific examples of the polycyclic aryl group include naphthyl, anthracenyl, phenanthryl, pyrenyl, perylenyl, klychenyl, fluorenyl, and the like.
  • the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.
  • the heterocyclic group includes at least one non-carbon atom or hetero atom, and specifically, the hetero atom may include at least one atom selected from the group consisting of O, N, Se and S, and the like.
  • the number of carbon atoms of the heterocyclic group is not particularly limited, but is preferably 2 to 60 carbon atoms.
  • heterocyclic group examples include thiophenyl group, furanyl group, pyrrolyl group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, triazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, A pyridazinyl group, a pyridopyrimidinyl group, a pyridopyrimidinyl group, a pyridazinyl group, a pyridazinyl group, a pyrimidinyl group, a pyrimidinyl group, a pyrimidinyl group, a pyrimidinyl group, a pyrimidinyl group, a pyrimidinyl group, A benzothiazolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a benzothiophenyl group,
  • Benzosilyl group Dibenzosilyl group. A phenanthrolinyl group, an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, a phenoxazinyl group, a condensed structure thereof, and the like, but are not limited thereto.
  • examples of the heterocyclic group include a heterocyclic structure including a sulfonyl group, .
  • Ar1 is a divalent substituted or unsubstituted heterocyclic group containing N.
  • Ar1 is 2-substituted or unsubstituted heterocyclic group containing 2 N atoms.
  • Ar1 is a divalent substituted heterocyclic group containing N.
  • Ar1 is a substituted or unsubstituted quinoline group; A substituted or unsubstituted quinazoline group; A substituted or unsubstituted phthalazine group; A substituted or unsubstituted quinoxaline group; Or a substituted or unsubstituted naphthyridyl group.
  • Ar1 is a substituted or unsubstituted quinazoline group; A substituted or unsubstituted phthalazine group; Or a substituted or unsubstituted quinoxaline group.
  • Ar1 is a substituted quinazoline group; A substituted phthalazine group; Or a substituted quinoxaline group.
  • Ar1 is a quinazoline group substituted with a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group; A phthalazine group substituted with a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group; Or a quinoxaline group substituted with a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.
  • substituted or unsubstituted of Ar < 1 > is deuterium; A nitrile group; An aryl group; And a heterocyclic group, which is substituted or unsubstituted.
  • the "substituted or unsubstituted" of Ar 1 is a phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; And an isoquinoline group, which are substituted or unsubstituted.
  • the "substituted or unsubstituted" of Ar1 is a phenyl group, a phenyl group substituted with deuterium, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, a phenyl group substituted with a phenanthrene group, A phenyl group substituted with a quinoline group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, a dibenzofurane group, A carbazole group substituted with a phenyl group, a carbazole group substituted with a biphenyl group, a carbazole group substituted with a naphth
  • Ar1 is represented by any one of the following formulas (2) to (5).
  • R21 to R25, R31 to R35, R41 to R45, and R51 to R55 are the same or different and independently of one another are hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • At least one of R21 to R25 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • one to three of R21 to R25 are substituted or unsubstituted aryl groups; Or a substituted or unsubstituted heterocyclic group.
  • one or two of R21 to R25 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • R21 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group; R22 to R25 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • At least one of R21 to R25 is a phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
  • At least one of R21 to R25 is a phenyl group substituted with a quinoline group, a phenyl group substituted with a quinoline group, a phenyl group substituted with a quinoline group, a phenyl group substituted with a naphthyl group, , A phenyl group substituted with a pyridine group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, a dibenzothiophene group, A carbazole group substituted with a phenyl group, a carbazole group substituted with a biphenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a quinoline
  • R21 is a phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, a borate or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
  • R21 is a phenyl group substituted with a phenyl group, a deuterium group, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, a phenyl group substituted with a phenanthrene group, a phenyl group substituted with a quinoline group, Substituted phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthrene group, triphenylene group, dimethylfluorene group, diphenylfluorene group, spirobifluorene group, dibenzofurane group, dibenzothiophene group and phenyl group A carbazole group substituted with a biphenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group
  • R 23 and R 24 are the same or different from each other, and each independently hydrogen; A phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
  • R 23 and R 24 are the same or different from each other and each independently represents a hydrogen, a phenyl group, a phenyl group substituted with deuterium, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, A phenyl group substituted with a quinoline group, a phenyl group substituted with a pyridine group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, A carbazole group substituted with a phenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group, a
  • R22 and R25 are hydrogen.
  • At least one of R31 to R35 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • one to three of R31 to R35 are substituted or unsubstituted aryl groups; Or a substituted or unsubstituted heterocyclic group.
  • one or two of R31 to R35 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • R31 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group; R32 to R35 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • At least one of R31 to R35 is a phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
  • At least one of R31 to R35 is selected from the group consisting of a phenyl group, a phenyl group substituted with deuterium, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, a phenyl group substituted with a phenanthrene group, , A phenyl group substituted with a pyridine group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, a dibenzothiophene group, A carbazole group substituted with a phenyl group, a carbazole group substituted with a biphenyl group, a carbazole group substituted with a naph
  • R31 is a phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, a nitro group or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
  • R31 is a phenyl group substituted with a phenyl group, a deuterium substituted phenyl group, a naphthyl group substituted phenyl group, a nitrile group substituted phenyl group, a phenanthrene group substituted phenyl group, a quinoline group substituted phenyl group, Substituted phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthrene group, triphenylene group, dimethylfluorene group, diphenylfluorene group, spirobifluorene group, dibenzofurane group, dibenzothiophene group and phenyl group A carbazole group substituted with a biphenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group, a pyr
  • R33 and R34 are the same or different from each other and each independently hydrogen; A phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
  • R33 and R34 are the same or different from each other and each independently represents a hydrogen, a phenyl group, a phenyl group substituted with deuterium, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, A phenyl group substituted with a quinoline group, a phenyl group substituted with a pyridine group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, A carbazole group substituted with a phenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group, a
  • R32 and R35 are hydrogen.
  • At least one of R41 to R45 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • At least one of R41 to R45 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • one or two of R41 to R45 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • R41 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group; R42 to R45 are the same or different from each other and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • At least one of R41 to R45 is a phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazole group substituted with an aryl group, a pyridine group, a quinoline group, or an isoquinoline group.
  • At least one of R41 to R45 is selected from the group consisting of a phenyl group, a phenyl group substituted with deuterium, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, a phenyl group substituted with a phenanthrene group, , A phenyl group substituted with a pyridine group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, a dibenzothiophene group, A carbazole group substituted with a phenyl group, a carbazole group substituted with a biphenyl group, a carbazole group substituted with a naph
  • R41 is a phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
  • R41 is a phenyl group substituted with a phenyl group, a deuterium group, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, a phenyl group substituted with a phenanthrene group, a phenyl group substituted with a quinoline group, Substituted phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthrene group, triphenylene group, dimethylfluorene group, diphenylfluorene group, spirobifluorene group, dibenzofurane group, dibenzothiophene group and phenyl group A carbazole group substituted with a biphenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group
  • R43 and R44 are the same or different and each independently hydrogen; A phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
  • R43 and R44 are the same or different and each independently represents a hydrogen, a phenyl group, a phenyl group substituted with deuterium, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, A phenyl group substituted with a quinoline group, a phenyl group substituted with a pyridine group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, A carbazole group substituted with a phenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group, a pyridine group
  • R42 and R45 are hydrogen.
  • At least one of R51 to R55 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • one to three of R51 to R55 are substituted or unsubstituted aryl groups; Or a substituted or unsubstituted heterocyclic group.
  • one or two of R51 to R55 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • R51 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, R52 to R55 are the same or different from each other and each independently represents hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • At least one of R51 to R55 is a phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
  • At least one of R 51 to R 55 is a phenyl group substituted with a quinoline group, a phenyl group substituted with a quinoline group, a phenyl group substituted with a quinoline group, a phenyl group substituted with a naphthyl group, , A phenyl group substituted with a pyridine group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, a dibenzothiophene group, A carbazole group substituted with a phenyl group, a carbazole group substituted with a biphenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a quinoline
  • R51 is a phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
  • R51 is a phenyl group substituted with a phenyl group, a deuterium group, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, a phenyl group substituted with a phenanthrene group, a phenyl group substituted with a quinoline group, Substituted phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthrene group, triphenylene group, dimethylfluorene group, diphenylfluorene group, spirobifluorene group, dibenzofurane group, dibenzothiophene group and phenyl group A carbazole group substituted with a biphenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group
  • R53 and R54 are the same or different and each independently hydrogen; A phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
  • R53 and R54 are the same or different and each independently represents a hydrogen, a phenyl group, a phenyl group substituted with deuterium, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, A phenyl group substituted with a quinoline group, a phenyl group substituted with a pyridine group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, A carbazole group substituted with a phenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group, a pyridine group
  • R52 and R55 are hydrogen.
  • X is S.
  • X is O.
  • L1 is a direct bond; A substituted or unsubstituted phenylene group; Or a substituted or unsubstituted naphthylene group.
  • L1 is a direct bond; A phenylene group; Or a naphthylene group.
  • L2 is a direct bond; A substituted or unsubstituted phenylene group; Or a substituted or unsubstituted naphthylene group.
  • L2 is a direct bond; A phenylene group; Or a naphthylene group.
  • L2 is a direct bond or a phenylene group.
  • R 1 and R 2 are the same or different and each independently hydrogen; Or an aryl group.
  • R 1 and R 2 are the same or different and each independently hydrogen; A phenyl group; Biphenyl group; Or a naphthyl group.
  • R1 and R2 are hydrogen.
  • R 3 and R 4 are the same or different from each other, and each independently hydrogen; An alkyl group; Or an aryl group.
  • R 3 and R 4 are the same or different from each other, and each independently hydrogen; Or an aryl group.
  • R 3 and R 4 are the same or different from each other, and each independently hydrogen; A phenyl group; Biphenyl group; Or a naphthyl group.
  • R3 and R4 are hydrogen.
  • the compound of Formula 1 is selected from the following structural formulas.
  • the compound of formula (1) according to one embodiment of the present application can be prepared by the following production method.
  • the compound of Formula 1 may be prepared in the same manner as in Preparation Example 1, below.
  • Substituent groups may be attached by methods known in the art, and the type, position or number of substituent groups may be varied according to techniques known in the art.
  • the compounds of the present invention can be prepared by using Buchwald-Hartwig coupling reaction, Heck coupling reaction, Suzuki coupling reaction and the like.
  • the solvent was removed by decompression. After that, it was completely dissolved in ethyl acetate, washed with water, and further decompressed to remove about 70% of the solvent.
  • the present invention also provides an organic electroluminescent device comprising the aforementioned compound.
  • the organic material layer of the organic electroluminescent device of the present application may have a single-layer structure, but may have a multilayer structure in which two or more organic material layers are stacked.
  • the organic electroluminescent device may have a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, etc. as an organic material layer.
  • the structure of the organic electroluminescent device is not limited thereto and may include a smaller number of organic layers.
  • the organic layer includes a light-emitting layer, and the light-emitting layer includes the compound of the general formula (1).
  • the organic layer includes a light emitting layer
  • the light emitting layer includes the compound of Formula 1
  • the light emitting layer is a red light emitting layer.
  • the organic layer includes a light emitting layer, and the light emitting layer includes a compound host of the formula (1).
  • the organic layer includes a light emitting layer, and the light emitting layer includes the compound red host of the formula (1).
  • the organic layer includes a light emitting layer, and the light emitting layer includes the compound of Formula 1 and a dopant.
  • the organic layer includes a light emitting layer, and the light emitting layer contains the compound of Formula 1 and the dopant in a weight ratio of 1: 1 to 100: 1.
  • the organic layer includes a light emitting layer, and the light emitting layer includes a dopant.
  • the organic layer includes a light emitting layer, the light emitting layer includes a dopant, and the dopant is a metal complex.
  • the organic layer includes a light emitting layer, the light emitting layer includes a dopant, and the dopant is an iridium metal complex.
  • the organic layer includes a light emitting layer
  • the dopant of the light emitting layer may be selected from the following structures.
  • the organic layer includes a light emitting layer, and the thickness of the light emitting layer is 100 to 700 ANGSTROM.
  • the organic layer includes a light emitting layer, and the thickness of the light emitting layer is 300 ANGSTROM to 500 ANGSTROM.
  • the organic layer includes a light emitting layer, and the thickness of the light emitting layer is 400 ANGSTROM.
  • the organic material layer includes a hole injecting layer or a hole transporting layer, and the hole injecting layer or the hole transporting layer includes the compound of the above formula (1).
  • the organic material layer includes a hole injecting layer, a hole transporting layer, or a hole injecting and transporting layer, and the hole injecting layer, the hole transporting layer, or the hole injecting and transporting layer includes the compound of Formula 1.
  • the organic layer includes a hole injection layer, and the hole injection layer is doped.
  • the organic layer includes a hole injection layer, and the hole injection layer is p-doped.
  • the organic layer includes an electron transporting layer or an electron injecting layer, and the electron transporting layer or the electron injecting layer includes the compound of the above formula (1).
  • the organic layer includes an electron injecting layer, an electron transporting layer, or an electron injecting and transporting layer, and the electron injecting layer, the electron transporting layer, or the electron injecting and transporting layer includes the compound of Formula 1.
  • the organic layer comprises an electron injection and transport layer
  • the electron injection and transport layer comprises lithium quinolate
  • the organic layer includes an electron blocking layer or a hole blocking layer
  • the electron blocking layer or the hole blocking layer includes the compound of the above formula (1).
  • the organic electroluminescent device includes a first electrode; A second electrode facing the first electrode; And a light emitting layer provided between the first electrode and the second electrode; And at least two organic layers disposed between the light emitting layer and the first electrode or between the light emitting layer and the second electrode, wherein the light emitting layer comprises the compound of Formula 1.
  • the two or more organic layers may be selected from the group consisting of a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, and an electron injecting and transporting layer.
  • the organic electroluminescent device may be a normal type organic light emitting device in which an anode, at least one organic layer, and a cathode are sequentially stacked on a substrate.
  • the organic electroluminescent device may be an inverted type organic light emitting device in which a cathode, at least one organic layer, and an anode are sequentially stacked on a substrate.
  • Figs. 1 and 2. For example, the structure of an organic electroluminescent device according to one embodiment of the present application is illustrated in Figs. 1 and 2. Fig.
  • FIG. 1 shows a structure of an organic electroluminescent device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially laminated.
  • the compound may be included in the light emitting layer (3).
  • Fig. 2 is a cross-sectional view showing the structure of a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, an electron blocking layer 7, a light emitting layer 3, a hole blocking layer 8, 9, and a cathode 4 are sequentially laminated on a transparent substrate 1, as shown in FIG.
  • the compound may be included in the light-emitting layer (3).
  • the compound may be contained in at least one of the hole injecting layer, the hole transporting layer, the light emitting layer, and the electron transporting layer.
  • the organic electroluminescent device of the present application can be produced by materials and methods known in the art, except that one or more of the organic layers include the compound of the present application, i.e., the compound.
  • the organic layers may be formed of the same material or different materials.
  • the organic light emitting device of the present application can be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate.
  • a PVD (physical vapor deposition) method such as a sputtering method or an e-beam evaporation method
  • a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate to form a positive electrode
  • an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer and an electron transporting layer thereon depositing a material usable as a cathode thereon.
  • an organic light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.
  • the compound of Formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum evaporation method in the production of an organic electroluminescent device.
  • the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating and the like, but is not limited thereto.
  • an organic electroluminescent device can also be fabricated by sequentially depositing an organic material layer and a cathode material on a substrate from a cathode material (International Patent Application Publication No. 2003/012890).
  • the manufacturing method is not limited thereto.
  • the first electrode is an anode and the second electrode is a cathode.
  • the first electrode is a cathode and the second electrode is a cathode.
  • the cathode material a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer.
  • the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO 2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.
  • the negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer.
  • Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as LiF / Al or LiO 2 / Al, but are not limited thereto.
  • the hole injecting layer is a layer for injecting holes from an electrode.
  • the hole injecting material has a hole injecting effect, and has a hole injecting effect on the light emitting layer or a light emitting material.
  • a compound which prevents the migration of excitons to the electron injecting layer or the electron injecting material and is also excellent in the thin film forming ability is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer.
  • HOMO highest occupied molecular orbital
  • the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.
  • the hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer.
  • the hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer.
  • the material is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.
  • the light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence.
  • Specific examples include 8-hydroxy-quinoline aluminum complex (Alq 3 ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.
  • the light emitting layer may include a host material and a dopant material.
  • the host material is a condensed aromatic ring derivative or a heterocyclic compound.
  • Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds.
  • Examples of heterocycle-containing compounds include compounds, dibenzofuran derivatives, ladder furan compounds , Pyrimidine derivatives, and the like, but are not limited thereto.
  • the electron transporting material is a layer that receives electrons from the electron injecting layer and transports electrons to the light emitting layer.
  • the electron transporting material is a material capable of transferring electrons from the cathode well to the light emitting layer. Is suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.
  • the electron transporting layer can be used with any desired cathode material as used according to the prior art.
  • an example of a suitable cathode material is a conventional material having a low work function followed by an aluminum layer or a silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.
  • the electron injection layer is a layer for injecting electrons from the electrode.
  • the electron injection layer has an ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron injection effect with respect to the light emitting layer or the light emitting material.
  • a compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable.
  • Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A complex compound and a nitrogen-containing five-membered ring derivative, but are not limited thereto.
  • Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.
  • the hole blocking layer prevents holes from reaching the cathode, and may be formed under the same conditions as those of the hole injecting layer. Specific examples thereof include, but are not limited to, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes and the like.
  • the organic electroluminescent device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.
  • the compound of Formula 3-79-a 18.55 g (1.0 eq ), dibenzo [b, d] furan-2-Daily acid 6.20 g (1.1 eq), Pd (t-Bu 3 P) 2 0.14 g (0.01 eq) in dioxane , And 11.28 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added thereto, followed by refluxing and stirring. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent.
  • the glass substrate coated with ITO (indium tin oxide) thin film with a thickness of 1,000 ⁇ was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, Fischer Co. product was used as a detergent, and distilled water, which was secondly filtered with a filter of Millipore Co., was used as distilled water.
  • the ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.
  • the following HI-1 compound was formed to a thickness of 1150 ANGSTROM as a hole injecting layer on the ITO transparent electrode thus prepared, and the following compound A-1 was p-doped at a concentration of 1.5%.
  • the following HT-1 compound was vacuum deposited on the hole injection layer to form a hole transport layer having a thickness of 800 ANGSTROM.
  • EB-1 compound having a thickness of 150 ANGSTROM was vacuum-deposited on the hole transport layer to form an electron blocking layer.
  • the following RH-1 compound and the following Dp-39 compound were vapor-deposited on the EB-1 vapor-deposited film at a weight ratio of 98: 2 to form a 400 ⁇ thick red light emitting layer.
  • HB-1 compound was vacuum deposited on the light emitting layer to a film thickness of 30 ANGSTROM to form a hole blocking layer. Subsequently, the following ET-1 compound and the following LiQ compound were vacuum-deposited on the hole blocking layer at a weight ratio of 2: 1 to form an electron injecting and transporting layer having a thickness of 300 ⁇ . Lithium fluoride (LiF) and aluminum having a thickness of 1,000 ⁇ were sequentially deposited on the electron injecting and transporting layer to form a cathode.
  • LiF lithium fluoride
  • aluminum having a thickness of 1,000 ⁇ were sequentially deposited on the electron injecting and transporting layer to form a cathode.
  • An organic electroluminescent device was produced in the same manner as in Comparative Example 1, except that the compound shown in the following Table 1 was used in place of RH-1 in the organic electroluminescent device of Comparative Example 1.
  • An organic electroluminescent device was produced in the same manner as in Comparative Example 1, except that the compound shown in the following Table 1 was used in place of RH-1 in the organic electroluminescent device of Comparative Example 1.
  • T95 means the time required for the luminance to decrease from the initial luminance (5000 nits) to 95%.
  • the compound of the present invention is superior in driving voltage and efficiency in an organic electroluminescent device as compared with a compound in which Ar1 is a monocyclic hetero ring containing N and X is C , And it was confirmed that it has superior characteristics particularly in terms of life span.

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Abstract

The present specification provides a compound of chemical formula 1 and an organic electroluminescent device comprising same.

Description

화합물 및 이를 포함하는 유기 전계 발광 소자Compound and organic electroluminescent device including same
본 명세서는 화합물 및 이를 포함하는 유기 전계 발광 소자에 관한 것이다.TECHNICAL FIELD The present invention relates to a compound and an organic electroluminescent device including the same.
본 명세서는 2017년 6월 23일에 한국특허청에 제출된 한국특허출원 제10-2017-0079703호의 출원일의 이익을 주장하며, 그 내용은 전부 본 명세서에 포함된다.This specification claims the benefit of Korean Patent Application No. 10-2017-0079703 filed on June 23, 2017, filed with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.
전계 발광 소자는 자체 발광형 표시 소자의 일종으로서, 시야각이 넓고, 콘트라스트가 우수할 뿐만 아니라 응답속도가 빠르다는 장점을 가지고 있다. An electroluminescent device is one type of self-luminous display device, and has advantages of wide viewing angle, excellent contrast, and high response speed.
유기발광소자는 2개의 전극 사이에 유기박막을 배치시킨 구조를 가지고 있다. 이와 같은 구조의 유기발광소자에 전압이 인가되면, 2개의 전극으로부터 주입된 전자와 정공이 유기박막에서 결합하여 쌍을 이룬 후 소멸하면서 빛을 발하게 된다. 상기 유기박막은 필요에 따라 단층 또는 다층으로 구성될 수 있다. The organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light emitting device having such a structure, electrons and holes injected from the two electrodes couple to each other in the organic thin film and form a pair, which then extinguishes and emits light. The organic thin film may be composed of a single layer or a multilayer, if necessary.
유기박막의 재료는 필요에 따라 발광 기능을 가질 수 있다. 예컨대, 유기박막 재료로는 그 자체가 단독으로 발광층을 구성할 수 있는 화합물이 사용될 수도 있고, 또는 호스트-도펀트계 발광층의 호스트 또는 도펀트 역할을 할 수 있는 화합물이 사용될 수도 있다. 그 외에도, 유기박막의 재료로서, 정공주입, 정공수송, 전자블록킹, 정공블록킹, 전자수송 또는 전자주입 등의 역할을 수행할 수 있는 화합물이 사용될 수도 있다.The material of the organic thin film may have a light emitting function as needed. For example, as the organic thin film material, a compound capable of forming a light emitting layer by itself may be used, or a compound capable of serving as a host or a dopant of a host-dopant light emitting layer may be used. In addition, as the material of the organic thin film, a compound capable of performing a role such as hole injection, hole transport, electron blocking, hole blocking, electron transport or electron injection may be used.
유기발광소자의 성능, 수명 또는 효율을 향상시키기 위하여, 유기박막의 재료의 개발이 지속적으로 요구되고 있다.In order to improve the performance, life or efficiency of an organic light emitting device, development of materials for organic thin films is continuously required.
본 명세서는 화합물 및 이를 포함하는 유기 전계 발광 소자를 제공한다.The present invention provides a compound and an organic electroluminescent device including the same.
본 출원은 하기 화학식 1로 표시되는 화합물을 제공한다. The present application provides a compound represented by the following general formula (1).
[화학식 1][Chemical Formula 1]
Figure PCTKR2018007083-appb-I000001
Figure PCTKR2018007083-appb-I000001
상기 화학식 1에 있어서, In Formula 1,
Ar1은 N을 포함하는 2환의 치환 또는 비치환된 헤테로고리기이고, Ar 1 is a divalent substituted or unsubstituted heterocyclic group containing N,
X는 O 또는 S이고, X is O or S,
L1 및 L2는 서로 같거나 상이하고, 각각 독립적으로 직접결합, 치환 또는 비치환된 아릴렌기, 또는 치환 또는 비치환된 2가의 헤테로고리기이며, L 1 and L 2 are the same or different from each other and are each independently a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted divalent heterocyclic group,
R1 내지 R4는 서로 같거나 상이하고, 각각 독립적으로 수소, 중수소, 할로겐기, 시아노기, 치환 또는 비치환된 알킬기, 치환 또는 비치환된 알콕시기, 치환 또는 비치환된 아릴기, 또는 치환 또는 비치환된 헤테로고리기이고, R 1 to R 4 are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, A substituted or unsubstituted heterocyclic group,
n은 0 내지 4의 정수이며, n이 2 이상인 경우 R1은 서로 같거나 상이하고,n is an integer of 0 to 4, and when n is 2 or more, R1 is the same or different from each other,
m은 0 내지 6의 정수이고, m이 2 이상인 경우 R2는 서로 같거나 상이하고,m is an integer of 0 to 6, and when m is 2 or more, R2 is the same or different,
o는 0 내지 3의 정수이고, o가 2 이상인 경우 R3는 서로 같거나 상이하고, o is an integer of 0 to 3, and when o is 2 or more, R3 is the same or different from each other,
p는 0 내지 4의 정수이고, p가 2 이상인 경우 R4는 서로 같거나 상이하고, p is an integer of 0 to 4, and when p is 2 or more, R4 is the same or different from each other,
0≤n+m≤9이다.0? N + m? 9.
또한, 본 출원은 제1 전극; 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자로서, 상기 유기물층 중 1층 이상은 전술한 화합물을 포함하는 것인 유기 전계 발광 소자를 제공한다. The present application also includes a first electrode; A second electrode facing the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the above-described compound.
본 출원의 일 실시상태에 따른 화합물은 유기 전계 발광 소자에 사용되어, 유기 전계 발광 소자의 구동전압을 낮추고, 광효율을 향상시키며, 화합물의 열적 안정서에 의하여 소자 수명 특성을 향상시킬 수 있다. The compound according to one embodiment of the present application is used in an organic electroluminescent device to lower the driving voltage of the organic electroluminescent device, to improve the light efficiency, and to improve the lifetime of the device by the thermal stability of the compound.
도 1은 기판(1), 양극(2), 발광층(3), 음극(4)이 순차적으로 적층된 유기 전계 발광 소자의 예를 도시한 것이다. Fig. 1 shows an example of an organic electroluminescent device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially laminated.
도 2는 기판 (1), 양극(2), 정공주입층(5), 정공수송층(6), 전자저지층(7),발광층(3), 정공저지층(8), 전자 주입 및 수송층(9) 및 음극(4)이 순차적으로 적층된 유기 전계 발광 소자의 예를 도시한 것이다.Fig. 2 is a cross-sectional view showing the structure of a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, an electron blocking layer 7, a light emitting layer 3, a hole blocking layer 8, 9) and a cathode 4 are sequentially laminated on a substrate 1.
도 3은 본 명세서의 일 실시상태에 따른 화학식 A의 1H-NMR data이다. FIG. 3 is 1H-NMR data of formula (A) according to one embodiment of the present invention.
도 4는 본 명세서의 일 실시상태에 따른 화학식 B의 1H-NMR data이다.4 is 1H-NMR data of formula (B) according to one embodiment of the present invention.
도 5는 본 명세서의 일 실시상태에 따른 화합물 1-30의 질량분석 스펙트럼이다.5 is a mass spectrometry spectrum of Compound 1-30 according to one embodiment of the present invention.
도 6은 본 명세서의 일 실시상태에 따른 화합물 2-96의 질량분석 스펙트럼이다.6 is a mass spectrometry spectrum of Compound 2-96 according to one embodiment of the present disclosure.
도 7은 본 명세서의 일 실시상태에 따른 화합물 3-37의 질량분석 스펙트럼이다.7 is a mass spectrometry spectrum of Compound 3-37 according to one embodiment of the present invention.
도 8은 본 명세서의 일 실시상태에 따른 화합물 4-57의 질량분석 스펙트럼이다.8 is a mass spectrometry spectrum of Compound 4-57 according to one embodiment of the present invention.
[부호의 설명][Description of Symbols]
1: 기판1: substrate
2: 양극2: anode
3: 발광층3: light emitting layer
4: 음극4: cathode
5: 정공주입층5: Hole injection layer
6: 정공수송6: Hole transport
7: 전자저지층7: Electronic blocking layer
8: 정공저지층8: hole blocking layer
9: 전자 주입 및 수송층9: Electron injection and transport layer
이하, 본 명세서에 대하여 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 명세서는 상기 화학식 1로 표시되는 화합물을 제공한다.The present invention provides a compound represented by the above formula (1).
본 명세서에 따른 상기 화학식 1로 표시되는 화합물은 벤조카바졸에 N을 포함하는 2환의 헤테로고리기가 결합함으로써, 전자 주입 및 수송 능력이 원활해지고, 디벤조퓨란기 및 디벤조티오펜기를 동시에 도입하여 입체적 장애를 발생시켜 분자간 집합체 형성을 방해하여, 유기발광소자 제작시에 구동전압 감소, 효율 및 수명의 특성이 향상된다. The compound represented by the general formula (1) according to the present invention is a compound in which two ring heterocyclic groups including N are bonded to benzocarbazole, so that the electron injecting and transporting ability becomes smooth and the dibenzofurane group and dibenzothiophene group are simultaneously introduced Steric hindrance is generated to interfere with the formation of an intermolecular aggregate, so that driving voltage reduction, efficiency and lifetime characteristics are improved in manufacturing an organic light emitting device.
본 명세서에서 치환기의 예시들은 아래에서 설명하나, 이에 한정되는 것은 아니다.Examples of substituents herein are described below, but are not limited thereto.
상기 "치환"이라는 용어는 화합물의 탄소 원자에 결합된 수소 원자가 다른 치환기로 바뀌는 것을 의미하며, 치환되는 위치는 수소 원자가 치환되는 위치 즉, 치환기가 치환 가능한 위치라면 한정하지 않으며, 2 이상 치환되는 경우, 2 이상의 치환기는 서로 동일하거나 상이할 수 있다.The term " substituted " means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the substituted position is not limited as long as the substituent is a substitutable position, , Two or more substituents may be the same as or different from each other.
본 명세서에서 "치환 또는 비치환된" 이라는 용어는 중수소; 할로겐기; 시아노기; 알킬기; 시클로알킬기; 알케닐기; 알콕시기; 치환 또는 비치환된 포스핀 옥사이드기; 아릴기; 및 헤테로고리기로 이루어진 군에서 선택된 1 또는 2 이상의 치환기로 치환되었거나 상기 예시된 치환기 중 2 이상의 치환기가 연결된 치환기로 치환되거나, 또는 어떠한 치환기도 갖지 않는 것을 의미한다. 예컨대, "2 이상의 치환기가 연결된 치환기"는 바이페닐기일 수 있다. 즉, 바이페닐기는 아릴기일 수도 있고, 2개의 페닐기가 연결된 치환기로 해석될 수 있다.As used herein, the term " substituted or unsubstituted " A halogen group; Cyano; An alkyl group; A cycloalkyl group; An alkenyl group; An alkoxy group; A substituted or unsubstituted phosphine oxide group; An aryl group; And a heterocyclic group, or that at least two of the substituents exemplified in the above exemplified substituents are substituted with a connected substituent, or have no substituent. For example, " a substituent to which at least two substituents are connected " may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.
본 명세서에 있어서, 할로겐기의 예로는 불소, 염소, 브롬 또는 요오드가 있다. In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.
본 명세서에 있어서, 상기 알킬기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나 1 내지 50인 것이 바람직하다. 구체적인 예로는 메틸, 에틸, 프로필, n-프로필, 이소프로필, 부틸, n-부틸, 이소부틸, tert-부틸, sec-부틸, 1-메틸-부틸, 1-에틸-부틸, 펜틸, n-펜틸, 이소펜틸, 네오펜틸, tert-펜틸, 헥실, n-헥실, 1-메틸펜틸, 2-메틸펜틸, 4-메틸-2-펜틸, 3,3-디메틸부틸, 2-에틸부틸, 헵틸, n-헵틸, 1-메틸헥실, 시클로펜틸메틸, 시클로헥실메틸, 옥틸, n-옥틸, tert-옥틸, 1-메틸헵틸, 2-에틸헥실, 2-프로필펜틸, n-노닐, 2,2-디메틸헵틸, 1-에틸-프로필, 1,1-디메틸-프로필, 이소헥실, 2-메틸펜틸, 4-메틸헥실, 5-메틸헥실 등이 있으나, 이들에 한정되지 않는다.In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec- N-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-hexyl, Cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like.
본 명세서에 있어서, 시클로알킬기는 특별히 한정되지 않으나, 탄소수 3 내지 60인 것이 바람직하며, 구체적으로 시클로프로필, 시클로부틸, 시클로펜틸, 3-메틸시클로펜틸, 2,3-디메틸시클로펜틸, 시클로헥실, 3-메틸시클로헥실, 4-메틸시클로헥실, 2,3-디메틸시클로헥실, 3,4,5-트리메틸시클로헥실, 4-tert-부틸시클로헥실, 시클로헵틸, 시클로옥틸 등이 있으나, 이에 한정되지 않는다. In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, But are not limited to, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert- butylcyclohexyl, cycloheptyl, Do not.
본 명세서에 있어서, 상기 알콕시기는 직쇄, 분지쇄 또는 고리쇄일 수 있다. 알콕시기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 20인 것이 바람직하다. 구체적으로, 메톡시, 에톡시, n-프로폭시, 이소프로폭시, n-부톡시, 이소부톡시, tert-부톡시, sec-부톡시, n-펜틸옥시, 네오펜틸옥시, 이소펜틸옥시, n-헥실옥시, 3,3-디메틸부틸옥시, 2-에틸부틸옥시, n-옥틸옥시, n-노닐옥시, n-데실옥시, 벤질옥시, p-메틸벤질옥시 등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n Butyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like. But is not limited thereto.
본 명세서에 있어서, 포스핀옥사이드기는 구체적으로 디페닐포스핀옥사이드기, 디나프틸포스핀옥사이드 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the phosphine oxide group specifically includes a diphenylphosphine oxide group, dinaphthylphosphine oxide, and the like, but is not limited thereto.
본 명세서에서 상기 아릴기가 단환식 아릴기인 경우 탄소수는 특별히 한정되지 않으나, 탄소수 6 내지 25인 것이 바람직하다. 구체적으로 단환식 아릴기로는 페닐기, 바이페닐기, 터페닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. In the present specification, when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 25 carbon atoms. Specific examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group, and the like, but are not limited thereto.
상기 아릴기가 다환식 아릴기인 경우 탄소수는 특별히 한정되지 않으나. 탄소수 10 내지 24인 것이 바람직하다. 구체적으로 다환식 아릴기로는 나프틸기, 안트라세닐기, 페난트릴기, 파이레닐기, 페릴레닐기, 크라이세닐기, 플루오레닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다.When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. And preferably has 10 to 24 carbon atoms. Specific examples of the polycyclic aryl group include naphthyl, anthracenyl, phenanthryl, pyrenyl, perylenyl, klychenyl, fluorenyl, and the like.
본 명세서에 있어서, 상기 플루오레닐기는 치환될 수 있으며, 인접한 치환기들이 서로 결합하여 고리를 형성할 수 있다.In the present specification, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.
상기 플루오레닐기가 치환되는 경우,
Figure PCTKR2018007083-appb-I000002
,
Figure PCTKR2018007083-appb-I000003
,
Figure PCTKR2018007083-appb-I000004
,
Figure PCTKR2018007083-appb-I000005
등이 될 수 있으나, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,
Figure PCTKR2018007083-appb-I000002
,
Figure PCTKR2018007083-appb-I000003
,
Figure PCTKR2018007083-appb-I000004
,
Figure PCTKR2018007083-appb-I000005
And the like, but the present invention is not limited thereto.
본 명세서에 있어서, 헤테로고리기는 탄소가 아닌 원자, 이종원자를 1 이상 포함하는 것으로서, 구체적으로 상기 이종 원자는 O, N, Se 및 S 등으로 이루어진 군에서 선택되는 원자를 1 이상 포함할 수 있다. 헤테로고리기의 탄소수는 특별히 한정되지 않으나, 탄소수 2 내지 60인 것이 바람직하다. 헤테로고리기의 예로는 티오페닐기, 퓨라닐기, 피롤기, 이미다졸릴기, 티아졸릴기, 옥사졸릴기, 옥사디아졸릴기, 트리아졸릴기, 피리딜기, 비피리딜기, 피리미딜기, 트리아지닐기, 아크리딜기, 하이드로아크리딜기, 피리다지닐기, 피라지닐기, 퀴놀리닐기, 퀴나졸리닐기, 퀴녹살리닐기, 프탈라지닐기, 피리도피리미디닐기, 피리도피라지닐기, 피라지노피라지닐기, 이소퀴놀리닐기, 인돌기, 카바졸릴기, 벤즈옥사졸릴기, 벤즈이미다졸릴기, 벤조티아졸릴기, 벤조카바졸릴기, 디벤조카바졸릴기, 벤조티오페닐기, 디벤조티오페닐기, 벤조퓨라닐기, 디벤조퓨라닐기. 벤조실롤기. 디벤조실롤기. 페난트롤리닐기(phenanthrolinyl group), 이소옥사졸릴기, 티아디아졸릴기, 페노티아지닐기, 페노옥사지닐기, 및 이들의 축합구조 등이 있으나, 이들에만 한정되는 것은 아니다. 이외에도 헤테로고리기의 예로서, 술포닐기를 포함하는 헤테로고리 구조, 예컨대,
Figure PCTKR2018007083-appb-I000006
등이 있다.In the present specification, the heterocyclic group includes at least one non-carbon atom or hetero atom, and specifically, the hetero atom may include at least one atom selected from the group consisting of O, N, Se and S, and the like. The number of carbon atoms of the heterocyclic group is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophenyl group, furanyl group, pyrrolyl group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, triazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, A pyridazinyl group, a pyridopyrimidinyl group, a pyridopyrimidinyl group, a pyridazinyl group, a pyridazinyl group, a pyrimidinyl group, a pyrimidinyl group, a pyrimidinyl group, a pyrimidinyl group, A benzothiazolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a benzothiophenyl group, a dibenzoyl group, a benzothiophenyl group, a benzothiophenyl group, a benzothiophenyl group, a benzothiophenyl group, a benzoimidazolyl group, A thiophenyl group, a benzofuranyl group, and a dibenzofuranyl group. Benzosilyl group. Dibenzosilyl group. A phenanthrolinyl group, an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, a phenoxazinyl group, a condensed structure thereof, and the like, but are not limited thereto. In addition, examples of the heterocyclic group include a heterocyclic structure including a sulfonyl group,
Figure PCTKR2018007083-appb-I000006
.
본 명세서의 일 실시상태에 있어서, 상기 Ar1은 N을 포함하는 2환의 치환 또는 비치환된 헤테로고리기이다. In one embodiment of the present specification, Ar1 is a divalent substituted or unsubstituted heterocyclic group containing N.
본 명세서의 일 실시상태에 있어서, 상기 Ar1은 2개의 N을 포함하고 2환의 치환 또는 비치환된 헤테로고리기이다. In one embodiment of the present specification, Ar1 is 2-substituted or unsubstituted heterocyclic group containing 2 N atoms.
본 명세서의 일 실시상태에 있어서, 상기 Ar1은 N을 포함하는 2환의 치환된 헤테로고리기이다. In one embodiment of the present specification, Ar1 is a divalent substituted heterocyclic group containing N.
본 명세서의 일 실시상태에 있어서, 상기 Ar1은 치환 또는 비치환된 퀴놀린기; 치환 또는 비치환된 퀴나졸린기; 치환 또는 비치환된 프탈라진기; 치환 또는 비치환된 퀴녹살린기; 또는 치환 또는 비치환된 나프틸라딘기이다.In one embodiment of the present specification, Ar1 is a substituted or unsubstituted quinoline group; A substituted or unsubstituted quinazoline group; A substituted or unsubstituted phthalazine group; A substituted or unsubstituted quinoxaline group; Or a substituted or unsubstituted naphthyridyl group.
본 명세서의 일 실시상태에 있어서, 상기 Ar1은 치환 또는 비치환된 퀴나졸린기; 치환 또는 비치환된 프탈라진기; 또는 치환 또는 비치환된 퀴녹살린기이다.In one embodiment of the present specification, Ar1 is a substituted or unsubstituted quinazoline group; A substituted or unsubstituted phthalazine group; Or a substituted or unsubstituted quinoxaline group.
본 명세서의 일 실시상태에 있어서, 상기 Ar1은 치환된 퀴나졸린기; 치환된 프탈라진기; 또는 치환된 퀴녹살린기이다.In one embodiment of the present specification, Ar1 is a substituted quinazoline group; A substituted phthalazine group; Or a substituted quinoxaline group.
본 명세서의 일 실시상태에 있어서, 상기 Ar1은 치환 또는 비치환된 아릴기 또는 치환 또는 비치환된 헤테로고리기로 치환된 퀴나졸린기; 치환 또는 비치환된 아릴기 또는 치환 또는 비치환된 헤테로고리기로 치환된 프탈라진기; 또는 치환 또는 비치환된 아릴기 또는 치환 또는 비치환된 헤테로고리기로 치환된 퀴녹살린기이다.In one embodiment of the present invention, Ar1 is a quinazoline group substituted with a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group; A phthalazine group substituted with a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group; Or a quinoxaline group substituted with a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 Ar1의 "치환 또는 비치환된"은 중수소; 니트릴기; 아릴기; 및 헤테로고리기로 이루어진 군에서 선택되는 1이상의 치환기로 치환 또는 비치환되는 것을 의미한다.In one embodiment herein, " substituted or unsubstituted " of Ar < 1 > is deuterium; A nitrile group; An aryl group; And a heterocyclic group, which is substituted or unsubstituted.
본 명세서의 일 실시상태에 있어서, 상기 Ar1의 "치환 또는 비치환된"은 중수소, 니트릴기, 아릴기, 또는 헤테로고리기로 치환 또는 비치환된 페닐기; 비페닐기; 터페닐기; 나프틸기; 페난쓰렌기; 트리페닐렌기; 알킬기 또는 아릴기로 치환 또는 비치환된 플루오렌기; 스피로비플루오렌기; 디벤조퓨란기; 디벤조티오펜기; 아릴기로 치환 또는 비치환된 카바졸기; 아릴기로 치환 또는 비치환된 벤조카바졸기; 피리딘기; 퀴놀린기; 및 이소퀴놀린기로 이루어진 군에서 선택되는 1이상의 치환기로 치환 또는 비치환되는 것을 의미한다.In one embodiment of the present specification, the "substituted or unsubstituted" of Ar 1 is a phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; And an isoquinoline group, which are substituted or unsubstituted.
본 명세서의 일 실시상태에 있어서, 상기 Ar1의 "치환 또는 비치환된"은 페닐기, 중수소로 치환된 페닐기, 나프틸기로 치환된 페닐기, 니트릴기로 치환된 페닐기, 페난쓰렌기로 치환된 페닐기, 피리딘기로 치환된 페닐기, 퀴놀린기로 치환된 페닐기, 비페닐기, 터페닐기, 나프틸기, 페난쓰렌기, 트리페닐렌기, 디메틸플루오렌기, 디페닐플루오렌기, 스피로비플루오렌기, 디벤조퓨란기, 디벤조티오펜기, 페닐기로 치환된 카바졸기, 비페닐기로 치환된 카바졸기, 나프틸기로 치환된 카바졸기, 페닐기로 치환된 벤조카바졸기, 피리딘기, 퀴놀린기, 및 이소퀴놀린기로 이루어진 군에서 선택되는 1이상의 치환기로 치환 또는 비치환되는 것을 의미한다.In one embodiment of the present specification, the "substituted or unsubstituted" of Ar1 is a phenyl group, a phenyl group substituted with deuterium, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, a phenyl group substituted with a phenanthrene group, A phenyl group substituted with a quinoline group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, a dibenzofurane group, A carbazole group substituted with a phenyl group, a carbazole group substituted with a biphenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group, a pyridine group, a quinoline group, and an isoquinoline group ≪ / RTI > is substituted or unsubstituted.
본 명세서의 일 실시상태에 있어서, 상기 Ar1은 하기 화학식 2 내지 5 중 어느 하나로 표시된다. In one embodiment of the present invention, Ar1 is represented by any one of the following formulas (2) to (5).
[화학식 2](2)
Figure PCTKR2018007083-appb-I000007
Figure PCTKR2018007083-appb-I000007
[화학식 3](3)
Figure PCTKR2018007083-appb-I000008
Figure PCTKR2018007083-appb-I000008
[화학식 4][Chemical Formula 4]
Figure PCTKR2018007083-appb-I000009
Figure PCTKR2018007083-appb-I000009
[화학식 5][Chemical Formula 5]
Figure PCTKR2018007083-appb-I000010
Figure PCTKR2018007083-appb-I000010
상기 화학식 2 내지 5에 있어서, In the above formulas 2 to 5,
Figure PCTKR2018007083-appb-I000011
은 상기 화학식 1의 L1과 결합하는 위치를 의미하고,
Figure PCTKR2018007083-appb-I000011
Refers to a position at which L < 1 > in formula (1)
R21 내지 R25, R31 내지 R35, R41 내지 R45, 및 R51 내지 R55는 서로 같거나 상이하고, 서로 독립적으로 수소; 중수소; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다. R21 to R25, R31 to R35, R41 to R45, and R51 to R55 are the same or different and independently of one another are hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 R21 내지 R25 중 적어도 하나는 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다.  In one embodiment of the present invention, at least one of R21 to R25 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 R21 내지 R25 중 1개 내지 3개는 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다.In one embodiment of the present specification, one to three of R21 to R25 are substituted or unsubstituted aryl groups; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 R21 내지 R25 중 1개 또는 2개는 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다.In one embodiment of the present specification, one or two of R21 to R25 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 R21은 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이고, 상기 R22 내지 R25는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다. In one embodiment of the present specification, R21 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group; R22 to R25 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 R21 내지 R25 중 적어도 하나는 중수소, 니트릴기, 아릴기, 또는 헤테로고리기로 치환 또는 비치환된 페닐기; 비페닐기; 터페닐기; 나프틸기; 페난쓰렌기; 트리페닐렌기; 알킬기 또는 아릴기로 치환 또는 비치환된 플루오렌기; 스피로비플루오렌기; 디벤조퓨란기; 디벤조티오펜기; 아릴기로 치환 또는 비치환된 카바졸기; 아릴기로 치환 또는 비치환된 벤조카바졸기; 피리딘기; 퀴놀린기; 또는 이소퀴놀린기이다. In one embodiment of the present invention, at least one of R21 to R25 is a phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R21 내지 R25 중 적어도 하나는 페닐기, 중수소로 치환된 페닐기, 나프틸기로 치환된 페닐기, 니트릴기로 치환된 페닐기, 페난쓰렌기로 치환된 페닐기, 퀴놀린기로 치환된 페닐기, 피리딘기로 치환된 페닐기, 비페닐기, 터페닐기, 나프틸기, 페난쓰렌기, 트리페닐렌기, 디메틸플루오렌기, 디페닐플루오렌기, 스피로비플루오렌기, 디벤조퓨란기, 디벤조티오펜기, 페닐기로 치환된 카바졸기, 비페닐기로 치환된 카바졸기, 나프틸기로 치환된 카바졸기, 페닐기로 치환된 벤조카바졸기, 피리딘기, 퀴놀린기, 또는 이소퀴놀린기이다.In one embodiment of the present invention, at least one of R21 to R25 is a phenyl group substituted with a quinoline group, a phenyl group substituted with a quinoline group, a phenyl group substituted with a quinoline group, a phenyl group substituted with a naphthyl group, , A phenyl group substituted with a pyridine group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, a dibenzothiophene group, A carbazole group substituted with a phenyl group, a carbazole group substituted with a biphenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group, a pyridine group, a quinoline group, or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R21은 중수소, 니트릴기, 아릴기,로 치또는 헤테로고리기로 치환 또는 비치환된 페닐기; 비페닐기; 터페닐기; 나프틸기; 페난쓰렌기; 트리페닐렌기; 알킬기 또는 아릴기로 치환 또는 비치환된 플루오렌기; 스피로비플루오렌기; 디벤조퓨란기; 디벤조티오펜기; 아릴기로 치환 또는 비치환된 카바졸기; 아릴기로 치환 또는 비치환된 벤조카바졸기; 피리딘기; 퀴놀린기; 또는 이소퀴놀린기이다. In one embodiment of the present specification, R21 is a phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, a borate or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R21은 페닐기, 중수소로 치환된 페닐기, 나프틸기로 치환된 페닐기, 니트릴기로 치환된 페닐기, 페난쓰렌기로 치환된 페닐기, 퀴놀린기로 치환된 페닐기, 피리딘기로 치환된 페닐기, 비페닐기, 터페닐기, 나프틸기, 페난쓰렌기, 트리페닐렌기, 디메틸플루오렌기, 디페닐플루오렌기, 스피로비플루오렌기, 디벤조퓨란기, 디벤조티오펜기, 페닐기로 치환된 카바졸기, 비페닐기로 치환된 카바졸기, 나프틸기로 치환된 카바졸기, 페닐기로 치환된 벤조카바졸기, 피리딘기, 퀴놀린기, 또는 이소퀴놀린기이다.In one embodiment of the present invention, R21 is a phenyl group substituted with a phenyl group, a deuterium group, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, a phenyl group substituted with a phenanthrene group, a phenyl group substituted with a quinoline group, Substituted phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthrene group, triphenylene group, dimethylfluorene group, diphenylfluorene group, spirobifluorene group, dibenzofurane group, dibenzothiophene group and phenyl group A carbazole group substituted with a biphenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group, a pyridine group, a quinoline group, or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R23 및 R24는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소, 니트릴기, 아릴기, 또는 헤테로고리기로 치환 또는 비치환된 페닐기; 비페닐기; 터페닐기; 나프틸기; 페난쓰렌기; 트리페닐렌기; 알킬기 또는 아릴기로 치환 또는 비치환된 플루오렌기; 스피로비플루오렌기; 디벤조퓨란기; 디벤조티오펜기; 아릴기로 치환 또는 비치환된 카바졸기; 아릴기로 치환 또는 비치환된 벤조카바졸기; 피리딘기; 퀴놀린기; 또는 이소퀴놀린기이다. In one embodiment of the present specification, R 23 and R 24 are the same or different from each other, and each independently hydrogen; A phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R23 및 R24는 서로 같거나 상이하고, 각각 독립적으로 수소, 페닐기, 중수소로 치환된 페닐기, 나프틸기로 치환된 페닐기, 니트릴기로 치환된 페닐기, 페난쓰렌기로 치환된 페닐기, 퀴놀린기로 치환된 페닐기, 피리딘기로 치환된 페닐기, 비페닐기, 터페닐기, 나프틸기, 페난쓰렌기, 트리페닐렌기, 디메틸플루오렌기, 디페닐플루오렌기, 스피로비플루오렌기, 디벤조퓨란기, 디벤조티오펜기, 페닐기로 치환된 카바졸기, 비페닐기로 치환된 카바졸기, 나프틸기로 치환된 카바졸기, 페닐기로 치환된 벤조카바졸기, 피리딘기, 퀴놀린기, 또는 이소퀴놀린기이다.In one embodiment of the present invention, R 23 and R 24 are the same or different from each other and each independently represents a hydrogen, a phenyl group, a phenyl group substituted with deuterium, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, A phenyl group substituted with a quinoline group, a phenyl group substituted with a pyridine group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, A carbazole group substituted with a phenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group, a pyridine group, a quinoline group, or an isoquinoline group substituted with a phenyl group, .
본 명세서의 일 실시상태에 있어서, 상기 R22 및 R25는 수소이다.In one embodiment of the present specification, R22 and R25 are hydrogen.
본 명세서의 일 실시상태에 있어서, 상기 R31 내지 R35 중 적어도 하나는 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다. In one embodiment of the present invention, at least one of R31 to R35 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 R31 내지 R35 중 1개 내지 3개는 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다. In one embodiment of the present specification, one to three of R31 to R35 are substituted or unsubstituted aryl groups; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 R31 내지 R35 중 1개 또는 2개는 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다.In one embodiment of the present invention, one or two of R31 to R35 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 R31은 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이고, 상기 R32 내지 R35는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다. In one embodiment of the present specification, R31 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group; R32 to R35 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 R31 내지 R35 중 적어도 하나는 중수소, 니트릴기, 아릴기, 또는 헤테로고리기로 치환 또는 비치환된 페닐기; 비페닐기; 터페닐기; 나프틸기; 페난쓰렌기; 트리페닐렌기; 알킬기 또는 아릴기로 치환 또는 비치환된 플루오렌기; 스피로비플루오렌기; 디벤조퓨란기; 디벤조티오펜기; 아릴기로 치환 또는 비치환된 카바졸기; 아릴기로 치환 또는 비치환된 벤조카바졸기; 피리딘기; 퀴놀린기; 또는 이소퀴놀린기이다. In one embodiment of the present invention, at least one of R31 to R35 is a phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R31 내지 R35 중 적어도 하나는 페닐기, 중수소로 치환된 페닐기, 나프틸기로 치환된 페닐기, 니트릴기로 치환된 페닐기, 페난쓰렌기로 치환된 페닐기, 퀴놀린기로 치환된 페닐기, 피리딘기로 치환된 페닐기, 비페닐기, 터페닐기, 나프틸기, 페난쓰렌기, 트리페닐렌기, 디메틸플루오렌기, 디페닐플루오렌기, 스피로비플루오렌기, 디벤조퓨란기, 디벤조티오펜기, 페닐기로 치환된 카바졸기, 비페닐기로 치환된 카바졸기, 나프틸기로 치환된 카바졸기, 페닐기로 치환된 벤조카바졸기, 피리딘기, 퀴놀린기, 또는 이소퀴놀린기이다.In one embodiment of the present invention, at least one of R31 to R35 is selected from the group consisting of a phenyl group, a phenyl group substituted with deuterium, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, a phenyl group substituted with a phenanthrene group, , A phenyl group substituted with a pyridine group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, a dibenzothiophene group, A carbazole group substituted with a phenyl group, a carbazole group substituted with a biphenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group, a pyridine group, a quinoline group, or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R31은 중수소, 니트릴기, 아릴기,로 또는 헤테로고리기로 치환 또는 비치환된 페닐기; 비페닐기; 터페닐기; 나프틸기; 페난쓰렌기; 트리페닐렌기; 알킬기 또는 아릴기로 치환 또는 비치환된 플루오렌기; 스피로비플루오렌기; 디벤조퓨란기; 디벤조티오펜기; 아릴기로 치환 또는 비치환된 카바졸기; 아릴기로 치환 또는 비치환된 벤조카바졸기; 피리딘기; 퀴놀린기; 또는 이소퀴놀린기이다. In one embodiment of the present invention, R31 is a phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, a nitro group or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R31은 페닐기, 중수소로 치환된 페닐기, 나프틸기로 치환된 페닐기, 니트릴기로 치환된 페닐기, 페난쓰렌기로 치환된 페닐기, 퀴놀린기로 치환된 페닐기, 피리딘기로 치환된 페닐기, 비페닐기, 터페닐기, 나프틸기, 페난쓰렌기, 트리페닐렌기, 디메틸플루오렌기, 디페닐플루오렌기, 스피로비플루오렌기, 디벤조퓨란기, 디벤조티오펜기, 페닐기로 치환된 카바졸기, 비페닐기로 치환된 카바졸기, 나프틸기로 치환된 카바졸기, 페닐기로 치환된 벤조카바졸기, 피리딘기, 퀴놀린기, 또는 이소퀴놀린기이다.In one embodiment of the present disclosure, R31 is a phenyl group substituted with a phenyl group, a deuterium substituted phenyl group, a naphthyl group substituted phenyl group, a nitrile group substituted phenyl group, a phenanthrene group substituted phenyl group, a quinoline group substituted phenyl group, Substituted phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthrene group, triphenylene group, dimethylfluorene group, diphenylfluorene group, spirobifluorene group, dibenzofurane group, dibenzothiophene group and phenyl group A carbazole group substituted with a biphenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group, a pyridine group, a quinoline group, or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R33 및 R34는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소, 니트릴기, 아릴기, 또는 헤테로고리기로 치환 또는 비치환된 페닐기; 비페닐기; 터페닐기; 나프틸기; 페난쓰렌기; 트리페닐렌기; 알킬기 또는 아릴기로 치환 또는 비치환된 플루오렌기; 스피로비플루오렌기; 디벤조퓨란기; 디벤조티오펜기; 아릴기로 치환 또는 비치환된 카바졸기; 아릴기로 치환 또는 비치환된 벤조카바졸기; 피리딘기; 퀴놀린기; 또는 이소퀴놀린기이다. In one embodiment of the present specification, R33 and R34 are the same or different from each other and each independently hydrogen; A phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R33 및 R34는 서로 같거나 상이하고, 각각 독립적으로 수소, 페닐기, 중수소로 치환된 페닐기, 나프틸기로 치환된 페닐기, 니트릴기로 치환된 페닐기, 페난쓰렌기로 치환된 페닐기, 퀴놀린기로 치환된 페닐기, 피리딘기로 치환된 페닐기, 비페닐기, 터페닐기, 나프틸기, 페난쓰렌기, 트리페닐렌기, 디메틸플루오렌기, 디페닐플루오렌기, 스피로비플루오렌기, 디벤조퓨란기, 디벤조티오펜기, 페닐기로 치환된 카바졸기, 비페닐기로 치환된 카바졸기, 나프틸기로 치환된 카바졸기, 페닐기로 치환된 벤조카바졸기, 피리딘기, 퀴놀린기, 또는 이소퀴놀린기이다.In one embodiment of the present specification, R33 and R34 are the same or different from each other and each independently represents a hydrogen, a phenyl group, a phenyl group substituted with deuterium, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, A phenyl group substituted with a quinoline group, a phenyl group substituted with a pyridine group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, A carbazole group substituted with a phenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group, a pyridine group, a quinoline group, or an isoquinoline group substituted with a phenyl group, .
본 명세서의 일 실시상태에 있어서, 상기 R32 및 R35는 수소이다.In one embodiment of the present specification, R32 and R35 are hydrogen.
본 명세서의 일 실시상태에 있어서, 상기 R41 내지 R45 중 적어도 하나는 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다. In one embodiment of the present invention, at least one of R41 to R45 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 R41 내지 R45 중 1개 내지 3개는치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다. In one embodiment of the present specification, at least one of R41 to R45 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 R41 내지 R45 중 1개 또는 2개는 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다.In one embodiment of the present specification, one or two of R41 to R45 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 R41은 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이고, 상기 R42 내지 R45는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다. In one embodiment of the present invention, R41 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group; R42 to R45 are the same or different from each other and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 R41 내지 R45 중 적어도 하나는 중수소, 니트릴기, 아릴기, 또는 헤테로고리기로 치환 또는 비치환된 페닐기; 비페닐기; 터페닐기; 나프틸기; 페난쓰렌기; 트리페닐렌기; 알킬기 또는 아릴기로 치환 또는 비치환된 플루오렌기; 스피로비플루오렌기; 디벤조퓨란기; 디벤조티오펜기; 아릴기로 치환 또는 비치환된 카바졸기; 아릴기로 치환 또는 비치환된 벤조카바졸기, 피리딘기, 퀴놀린기, 또는 이소퀴놀린기이다. In one embodiment of the present invention, at least one of R41 to R45 is a phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazole group substituted with an aryl group, a pyridine group, a quinoline group, or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R41 내지 R45 중 적어도 하나는 페닐기, 중수소로 치환된 페닐기, 나프틸기로 치환된 페닐기, 니트릴기로 치환된 페닐기, 페난쓰렌기로 치환된 페닐기, 퀴놀린기로 치환된 페닐기, 피리딘기로 치환된 페닐기, 비페닐기, 터페닐기, 나프틸기, 페난쓰렌기, 트리페닐렌기, 디메틸플루오렌기, 디페닐플루오렌기, 스피로비플루오렌기, 디벤조퓨란기, 디벤조티오펜기, 페닐기로 치환된 카바졸기, 비페닐기로 치환된 카바졸기, 나프틸기로 치환된 카바졸기, 페닐기로 치환된 벤조카바졸기, 피리딘기, 퀴놀린기, 또는 이소퀴놀린기이다.In one embodiment of the present invention, at least one of R41 to R45 is selected from the group consisting of a phenyl group, a phenyl group substituted with deuterium, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, a phenyl group substituted with a phenanthrene group, , A phenyl group substituted with a pyridine group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, a dibenzothiophene group, A carbazole group substituted with a phenyl group, a carbazole group substituted with a biphenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group, a pyridine group, a quinoline group, or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R41은 중수소, 니트릴기, 아릴기,또는 헤테로고리기로 치환 또는 비치환된 페닐기; 비페닐기; 터페닐기; 나프틸기; 페난쓰렌기; 트리페닐렌기; 알킬기 또는 아릴기로 치환 또는 비치환된 플루오렌기; 스피로비플루오렌기; 디벤조퓨란기; 디벤조티오펜기; 아릴기로 치환 또는 비치환된 카바졸기; 아릴기로 치환 또는 비치환된 벤조카바졸기; 피리딘기; 퀴놀린기; 또는 이소퀴놀린기이다. In one embodiment of the present specification, R41 is a phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R41은 페닐기, 중수소로 치환된 페닐기, 나프틸기로 치환된 페닐기, 니트릴기로 치환된 페닐기, 페난쓰렌기로 치환된 페닐기, 퀴놀린기로 치환된 페닐기, 피리딘기로 치환된 페닐기, 비페닐기, 터페닐기, 나프틸기, 페난쓰렌기, 트리페닐렌기, 디메틸플루오렌기, 디페닐플루오렌기, 스피로비플루오렌기, 디벤조퓨란기, 디벤조티오펜기, 페닐기로 치환된 카바졸기, 비페닐기로 치환된 카바졸기, 나프틸기로 치환된 카바졸기, 페닐기로 치환된 벤조카바졸기, 피리딘기, 퀴놀린기, 또는 이소퀴놀린기이다.In one embodiment of the present invention, R41 is a phenyl group substituted with a phenyl group, a deuterium group, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, a phenyl group substituted with a phenanthrene group, a phenyl group substituted with a quinoline group, Substituted phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthrene group, triphenylene group, dimethylfluorene group, diphenylfluorene group, spirobifluorene group, dibenzofurane group, dibenzothiophene group and phenyl group A carbazole group substituted with a biphenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group, a pyridine group, a quinoline group, or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R43 및 R44는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소, 니트릴기, 아릴기 또는 헤테로고리기로 치환 또는 비치환된 페닐기; 비페닐기; 터페닐기; 나프틸기; 페난쓰렌기; 트리페닐렌기; 알킬기 또는 아릴기로 치환 또는 비치환된 플루오렌기; 스피로비플루오렌기; 디벤조퓨란기; 디벤조티오펜기; 아릴기로 치환 또는 비치환된 카바졸기; 아릴기로 치환 또는 비치환된 벤조카바졸기; 피리딘기; 퀴놀린기; 또는 이소퀴놀린기이다. In one embodiment of the present specification, R43 and R44 are the same or different and each independently hydrogen; A phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R43 및 R44는 서로 같거나 상이하고, 각각 독립적으로 수소, 페닐기, 중수소로 치환된 페닐기, 나프틸기로 치환된 페닐기, 니트릴기로 치환된 페닐기, 페난쓰렌기로 치환된 페닐기, 퀴놀린기로 치환된 페닐기, 피리딘기로 치환된 페닐기, 비페닐기, 터페닐기, 나프틸기, 페난쓰렌기, 트리페닐렌기, 디메틸플루오렌기, 디페닐플루오렌기, 스피로비플루오렌기, 디벤조퓨란기, 디벤조티오펜기, 페닐기로 치환된 카바졸기, 비페닐기로 치환된 카바졸기, 나프틸기로 치환된 카바졸기, 페닐기로 치환된 벤조카바졸기, 피리딘기, 퀴놀린기, 또는 이소퀴놀린기이다.In one embodiment of the present invention, R43 and R44 are the same or different and each independently represents a hydrogen, a phenyl group, a phenyl group substituted with deuterium, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, A phenyl group substituted with a quinoline group, a phenyl group substituted with a pyridine group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, A carbazole group substituted with a phenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group, a pyridine group, a quinoline group, or an isoquinoline group substituted with a phenyl group, .
본 명세서의 일 실시상태에 있어서, 상기 R42 및 R45는 수소이다.In one embodiment of the present specification, R42 and R45 are hydrogen.
본 명세서의 일 실시상태에 있어서, 상기 R51 내지 R55 중 적어도 하나는 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다. In one embodiment of the present specification, at least one of R51 to R55 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 R51 내지 R55 중 1개 내지 3개는 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다. In one embodiment of the present specification, one to three of R51 to R55 are substituted or unsubstituted aryl groups; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 R51 내지 R55 중 1개 또는 2개는 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다.In one embodiment of the present specification, one or two of R51 to R55 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 R51은 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이고, 상기 R52 내지 R55는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다. In one embodiment of the present specification, R51 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, R52 to R55 are the same or different from each other and each independently represents hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 R51 내지 R55 중 적어도 하나는 중수소, 니트릴기, 아릴기 또는 헤테로고리기로 치환 또는 비치환된 페닐기; 비페닐기; 터페닐기; 나프틸기; 페난쓰렌기; 트리페닐렌기; 알킬기 또는 아릴기로 치환 또는 비치환된 플루오렌기; 스피로비플루오렌기; 디벤조퓨란기; 디벤조티오펜기; 아릴기로 치환 또는 비치환된 카바졸기; 아릴기로 치환 또는 비치환된 벤조카바졸기; 피리딘기; 퀴놀린기; 또는 이소퀴놀린기이다. In one embodiment of the present invention, at least one of R51 to R55 is a phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R51 내지 R55 중 적어도 하나는 페닐기, 중수소로 치환된 페닐기, 나프틸기로 치환된 페닐기, 니트릴기로 치환된 페닐기, 페난쓰렌기로 치환된 페닐기, 퀴놀린기로 치환된 페닐기, 피리딘기로 치환된 페닐기, 비페닐기, 터페닐기, 나프틸기, 페난쓰렌기, 트리페닐렌기, 디메틸플루오렌기, 디페닐플루오렌기, 스피로비플루오렌기, 디벤조퓨란기, 디벤조티오펜기, 페닐기로 치환된 카바졸기, 비페닐기로 치환된 카바졸기, 나프틸기로 치환된 카바졸기, 페닐기로 치환된 벤조카바졸기, 피리딘기, 퀴놀린기, 또는 이소퀴놀린기이다.In one embodiment of the present invention, at least one of R 51 to R 55 is a phenyl group substituted with a quinoline group, a phenyl group substituted with a quinoline group, a phenyl group substituted with a quinoline group, a phenyl group substituted with a naphthyl group, , A phenyl group substituted with a pyridine group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, a dibenzothiophene group, A carbazole group substituted with a phenyl group, a carbazole group substituted with a biphenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group, a pyridine group, a quinoline group, or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R51은 중수소, 니트릴기, 아릴기,또는 헤테로고리기로 치환 또는 비치환된 페닐기; 비페닐기; 터페닐기; 나프틸기; 페난쓰렌기; 트리페닐렌기; 알킬기 또는 아릴기로 치환 또는 비치환된 플루오렌기; 스피로비플루오렌기; 디벤조퓨란기; 디벤조티오펜기; 아릴기로 치환 또는 비치환된 카바졸기; 아릴기로 치환 또는 비치환된 벤조카바졸기; 피리딘기; 퀴놀린기; 또는 이소퀴놀린기이다. In one embodiment of the present invention, R51 is a phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R51은 페닐기, 중수소로 치환된 페닐기, 나프틸기로 치환된 페닐기, 니트릴기로 치환된 페닐기, 페난쓰렌기로 치환된 페닐기, 퀴놀린기로 치환된 페닐기, 피리딘기로 치환된 페닐기, 비페닐기, 터페닐기, 나프틸기, 페난쓰렌기, 트리페닐렌기, 디메틸플루오렌기, 디페닐플루오렌기, 스피로비플루오렌기, 디벤조퓨란기, 디벤조티오펜기, 페닐기로 치환된 카바졸기, 비페닐기로 치환된 카바졸기, 나프틸기로 치환된 카바졸기, 페닐기로 치환된 벤조카바졸기, 피리딘기, 퀴놀린기, 또는 이소퀴놀린기이다.In one embodiment of the present invention, R51 is a phenyl group substituted with a phenyl group, a deuterium group, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, a phenyl group substituted with a phenanthrene group, a phenyl group substituted with a quinoline group, Substituted phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthrene group, triphenylene group, dimethylfluorene group, diphenylfluorene group, spirobifluorene group, dibenzofurane group, dibenzothiophene group and phenyl group A carbazole group substituted with a biphenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group, a pyridine group, a quinoline group, or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R53 및 R54는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소, 니트릴기, 아릴기, 또는 헤테로고리기로 치환 또는 비치환된 페닐기; 비페닐기; 터페닐기; 나프틸기; 페난쓰렌기; 트리페닐렌기; 알킬기 또는 아릴기로 치환 또는 비치환된 플루오렌기; 스피로비플루오렌기; 디벤조퓨란기; 디벤조티오펜기; 아릴기로 치환 또는 비치환된 카바졸기; 아릴기로 치환 또는 비치환된 벤조카바졸기; 피리딘기; 퀴놀린기; 또는 이소퀴놀린기이다. In one embodiment of the present specification, R53 and R54 are the same or different and each independently hydrogen; A phenyl group substituted or unsubstituted with a deuterium, a nitrile group, an aryl group, or a heterocyclic group; Biphenyl group; A terphenyl group; Naphthyl group; Phenanthrene; Triphenylene group; A fluorene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorene group; A dibenzofurane group; A dibenzothiophene group; A carbazolyl group substituted or unsubstituted with an aryl group; A benzocarbazolyl group substituted or unsubstituted with an aryl group; A pyridine group; A quinoline group; Or an isoquinoline group.
본 명세서의 일 실시상태에 있어서, 상기 R53 및 R54는 서로 같거나 상이하고, 각각 독립적으로 수소, 페닐기, 중수소로 치환된 페닐기, 나프틸기로 치환된 페닐기, 니트릴기로 치환된 페닐기, 페난쓰렌기로 치환된 페닐기, 퀴놀린기로 치환된 페닐기, 피리딘기로 치환된 페닐기, 비페닐기, 터페닐기, 나프틸기, 페난쓰렌기, 트리페닐렌기, 디메틸플루오렌기, 디페닐플루오렌기, 스피로비플루오렌기, 디벤조퓨란기, 디벤조티오펜기, 페닐기로 치환된 카바졸기, 비페닐기로 치환된 카바졸기, 나프틸기로 치환된 카바졸기, 페닐기로 치환된 벤조카바졸기, 피리딘기, 퀴놀린기, 또는 이소퀴놀린기이다.In one embodiment of the present specification, R53 and R54 are the same or different and each independently represents a hydrogen, a phenyl group, a phenyl group substituted with deuterium, a phenyl group substituted with a naphthyl group, a phenyl group substituted with a nitrile group, A phenyl group substituted with a quinoline group, a phenyl group substituted with a pyridine group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a spirobifluorene group, A carbazole group substituted with a phenyl group, a carbazole group substituted with a naphthyl group, a benzocarbazole group substituted with a phenyl group, a pyridine group, a quinoline group, or an isoquinoline group substituted with a phenyl group, .
본 명세서의 일 실시상태에 있어서, 상기 R52 및 R55는 수소이다.In one embodiment of the present specification, R52 and R55 are hydrogen.
본 명세서의 일 실시상태에 있어서, 상기 X는 S이다. In one embodiment of the present disclosure, X is S.
본 명세서의 일 실시상태에 있어서, 상기 X는 O이다.In one embodiment of the present disclosure, X is O.
본 명세서의 일 실시상태에 있어서, 상기 L1은 직접결합; 치환 또는 비치환된 페닐렌기; 또는 치환 또는 비치환된 나프틸렌기이다. In one embodiment of the present disclosure, L1 is a direct bond; A substituted or unsubstituted phenylene group; Or a substituted or unsubstituted naphthylene group.
본 명세서의 일 실시상태에 있어서, 상기 L1은 직접결합; 페닐렌기; 또는 나프틸렌기이다. In one embodiment of the present disclosure, L1 is a direct bond; A phenylene group; Or a naphthylene group.
본 명세서의 일 실시상태에 있어서, 상기 L2는 직접결합; 치환 또는 비치환된 페닐렌기; 또는 치환 또는 비치환된 나프틸렌기이다. In one embodiment of the present disclosure, L2 is a direct bond; A substituted or unsubstituted phenylene group; Or a substituted or unsubstituted naphthylene group.
본 명세서의 일 실시상태에 있어서, 상기 L2는 직접결합; 페닐렌기; 또는 나프틸렌기이다. In one embodiment of the present disclosure, L2 is a direct bond; A phenylene group; Or a naphthylene group.
본 명세서의 일 실시상태에 있어서, 상기 L2은 직접결합 또는 페닐렌기이다.In one embodiment of the present specification, L2 is a direct bond or a phenylene group.
본 명세서의 일 실시상태에 있어서, 상기 R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 수소; 또는 아릴기이다.In one embodiment of the present specification, R 1 and R 2 are the same or different and each independently hydrogen; Or an aryl group.
본 명세서의 일 실시상태에 있어서, 상기 R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 수소; 페닐기; 비페닐기; 또는 나프틸기이다.In one embodiment of the present specification, R 1 and R 2 are the same or different and each independently hydrogen; A phenyl group; Biphenyl group; Or a naphthyl group.
본 명세서의 일 실시상태에 있어서, 상기 R1 및 R2는 수소이다.In one embodiment of the present disclosure, R1 and R2 are hydrogen.
본 명세서의 일 실시상태에 있어서, 상기 R3 및 R4는 서로 같거나 상이하고, 각각 독립적으로 수소; 알킬기; 또는 아릴기이다.In one embodiment of the present specification, R 3 and R 4 are the same or different from each other, and each independently hydrogen; An alkyl group; Or an aryl group.
본 명세서의 일 실시상태에 있어서, 상기 R3 및 R4는 서로 같거나 상이하고, 각각 독립적으로 수소; 또는 아릴기이다.In one embodiment of the present specification, R 3 and R 4 are the same or different from each other, and each independently hydrogen; Or an aryl group.
본 명세서의 일 실시상태에 있어서, 상기 R3 및 R4는 서로 같거나 상이하고, 각각 독립적으로 수소; 페닐기; 비페닐기; 또는 나프틸기이다.In one embodiment of the present specification, R 3 and R 4 are the same or different from each other, and each independently hydrogen; A phenyl group; Biphenyl group; Or a naphthyl group.
본 명세서의 일 실시상태에 있어서, 상기 R3 및 R4는 수소이다.In one embodiment of the present disclosure, R3 and R4 are hydrogen.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1의 화합물은 하기 구조식들 중에서 선택된다.In one embodiment of the present invention, the compound of Formula 1 is selected from the following structural formulas.
Figure PCTKR2018007083-appb-I000012
Figure PCTKR2018007083-appb-I000012
Figure PCTKR2018007083-appb-I000013
Figure PCTKR2018007083-appb-I000013
Figure PCTKR2018007083-appb-I000014
Figure PCTKR2018007083-appb-I000014
Figure PCTKR2018007083-appb-I000015
Figure PCTKR2018007083-appb-I000015
Figure PCTKR2018007083-appb-I000016
Figure PCTKR2018007083-appb-I000016
Figure PCTKR2018007083-appb-I000017
Figure PCTKR2018007083-appb-I000017
Figure PCTKR2018007083-appb-I000018
Figure PCTKR2018007083-appb-I000018
Figure PCTKR2018007083-appb-I000019
Figure PCTKR2018007083-appb-I000019
Figure PCTKR2018007083-appb-I000020
Figure PCTKR2018007083-appb-I000020
Figure PCTKR2018007083-appb-I000021
Figure PCTKR2018007083-appb-I000021
Figure PCTKR2018007083-appb-I000022
Figure PCTKR2018007083-appb-I000022
Figure PCTKR2018007083-appb-I000023
Figure PCTKR2018007083-appb-I000023
Figure PCTKR2018007083-appb-I000024
Figure PCTKR2018007083-appb-I000024
Figure PCTKR2018007083-appb-I000025
Figure PCTKR2018007083-appb-I000025
Figure PCTKR2018007083-appb-I000026
Figure PCTKR2018007083-appb-I000026
Figure PCTKR2018007083-appb-I000027
Figure PCTKR2018007083-appb-I000027
본 출원의 일 실시 상태에 따른 화학식 1의 화합물은 후술하는 제조방법으로 제조될 수 있다.The compound of formula (1) according to one embodiment of the present application can be prepared by the following production method.
예컨데 상기 화학식 1의 화합물은 하기 제조예 1과 같이 코어구조가 제조될수 있다. 치환기는 당기술분야에 알려져 있는 방법에 의하여 결합될 수 있으며, 치환기의 종류, 위치 또는 개수는 당기술분야에 알려져 있는 기술에 따라 변경될 수 있다.For example, the compound of Formula 1 may be prepared in the same manner as in Preparation Example 1, below. Substituent groups may be attached by methods known in the art, and the type, position or number of substituent groups may be varied according to techniques known in the art.
[제조예 1][Production Example 1]
Figure PCTKR2018007083-appb-I000028
Figure PCTKR2018007083-appb-I000028
본 발명의 화합물은 Buchwald-Hartwig coupling reaction, Heck coupling reaction, Suzuki coupling reaction 등을 이용하여 제조할 수 있다. The compounds of the present invention can be prepared by using Buchwald-Hartwig coupling reaction, Heck coupling reaction, Suzuki coupling reaction and the like.
1) 화학식 A-1의 제조1) Preparation of the compound of formula A-1
나프탈렌-2-아민 200.0 g (1.0 eq), 1-브로모-4-클로로-2-아이오도벤젠 443.25 g (1.0 eq), NaOtBu 201.3 g (1.5 eq), Pd(OAc)2 3.13 g (0.01 eq), 잔포스(Xantphos) 8.08 g (0.01 eq),1,4-다이옥산 4L 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 에틸아세테이트에 완전히 녹여서 물로 씻어주고 다시 감압하여 용매를 70% 정도 제거했다. 다시 환류 상태에서 헥산을 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 A-1 283.41 g (수율 61 %)를 얻었다. [M+H]=333Naphthalene-2-amine 200.0 g (1.0 eq), 1- bromo-4-chloro-2-iodo-benzene, 443.25 g (1.0 eq), NaOtBu 201.3 g (1.5 eq), Pd (OAc) 2 3.13 g (0.01 eq), 8.08 g (0.01 eq) of Xantphos and 4 L of 1,4-dioxane, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in ethyl acetate, washed with water, and further decompressed to remove about 70% of the solvent. Again, hexane was added in reflux, the crystals were dropped, cooled and filtered. This was subjected to column chromatography to obtain 283.41 g (yield: 61%) of Compound A-1. [M + H] < + > = 333
2) 화학식 A (3-클로로-5H-벤조[b]카바졸)의 제조2) Preparation of the formula A (3-chloro-5H-benzo [b] carbazole)
화학식 A-1 283.41 g (1.0 eq) 에 Pd(t-Bu3P)2 3.90 g (0.01 eq), K2CO3 211.11 g (2.00 eq) 을 다이에틸아세트아마이드 (Dimethylacetamide) 2L에 넣고 환류하여 교반했다. 3시간 후 반응물을 물에 부어서 결정을 떨어트리고 여과했다. 여과한 고체를 1,2-디클로로벤젠에 완전히 녹인 후 물로 씻어주고 생성물이 녹아있는 용액을 감압 농축하여 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피로 정제하여 화학식 A (3-클로로-5H-벤조[b]카바졸)74.97 g (수율 39 %)을 얻었다. 화학식 A의 1H-NMR 측정 그래프를 도 3에 나타내었다. [M+H]=252To 283.41 g (1.0 eq) of formula A-1 was added Pd (t-Bu 3 P) 2 3.90 g (0.01 eq) of K 2 CO 3 and 211.11 g (2.00 eq) of K 2 CO 3 were placed in 2 L of dimethylacetamide, refluxed and stirred. After 3 hours, the reaction mixture was poured into water, and crystals were dropped and filtered. The filtered solid was completely dissolved in 1,2-dichlorobenzene, washed with water, and the solution in which the product was dissolved was concentrated under reduced pressure to precipitate crystals, which were then cooled and then filtered. This was purified by column chromatography to obtain 74.97 g (yield 39%) of a compound represented by the formula A (3-chloro-5H-benzo [b] carbazole). The 1 H-NMR measurement graph of the formula (A) is shown in FIG. [M + H] < + > = 252
제조예 2. 화학식 B (2-클로로-5H-벤조[b]카바졸)의 제조 Preparation 2. Preparation of (B) (2-chloro-5H-benzo [b] carbazole)
1-브로모-4-클로로-2-아이오도벤젠 대신 2-브로모-4-클로로-1-아이오도벤젠 을 사용하여 화학식 A의 제조 방법과 같은 방법으로 2-클로로-5H-벤조[b]카바졸을 합성했다. 화학식 B의 1H-NMR 측정 그래프를 도 4에 나타내었다. [M+H]=252Bromo-4-chloro-1-iodobenzene in place of 1-bromo-4-chloro-2-iodobenzene, 2-chloro-5H-benzo [b ] Carbazole was synthesized. The 1 H-NMR measurement graph of Formula B is shown in FIG. [M + H] < + > = 252
Figure PCTKR2018007083-appb-I000029
Figure PCTKR2018007083-appb-I000029
제조예 3. 화학식 C (1-클로로-5H-벤조[b]카바졸) 의 제조 Preparation 3. Preparation of the formula C (1-Chloro-5H-benzo [b] carbazole)
1-브로모-4-클로로-2-아이오도벤젠 대신 2-브로모-1-클로로-3-아이오도벤젠을 사용하여 화학식 A의 제조 방법과 같은 방법으로 1-클로로-5H-벤조[b]카바졸을 합성했다.Bromo-1-chloro-3-iodobenzene in place of 1-bromo-4-chloro-2-iodobenzene, 1- chloro- ] Carbazole was synthesized.
Figure PCTKR2018007083-appb-I000030
Figure PCTKR2018007083-appb-I000030
제조예 4. 화학식 D (4-클로로-5H-벤조[b]카바졸) 의 제조 Preparation 4. Preparation of the formula D (4-chloro-5H-benzo [b] carbazole)
1-브로모-4-클로로-2-아이오도벤젠 대신 1-브로모-3-클로로-2-아이오도벤젠을 사용하여 화학식 A의 제조 방법과 같은 방법으로 4-클로로-5H-벤조[b]카바졸을 합성했다.Bromo-3-chloro-2-iodobenzene instead of 1-bromo-4-chloro-2-iodobenzene, 4-chloro-5H-benzo [b ] Carbazole was synthesized.
Figure PCTKR2018007083-appb-I000031
Figure PCTKR2018007083-appb-I000031
제조예 5. 화학식 E (9-클로로-5H-벤조[b]카바졸) 제조 Preparation 5. Preparation of the compound of formula E (9-chloro-5H-benzo [b] carbazole)
나프탈렌-2-아민 대신 6-클로로나프탈렌-2-아민, 1-브로모-4-클로로-2-아이오도벤젠 대신 1-브로모-2-아이오도벤젠을 사용하여 화학식 A의 제조 방법과 같은 방법으로 9-클로로-5H-벤조[b]카바졸을 합성했다.Bromo-2-iodobenzene instead of 6-chloronaphthalene-2-amine and 1-bromo-4-chloro-2-iodobenzene in place of naphthalene- 9-chloro-5H-benzo [b] carbazole was synthesized.
Figure PCTKR2018007083-appb-I000032
Figure PCTKR2018007083-appb-I000032
제조예 6. 화학식 F (8-클로로-5H-벤조[b]카바졸) 제조 Preparation 6. Preparation of the compound of formula F (8-chloro-5H-benzo [b] carbazole)
나프탈렌-2-아민 대신 7-클로로나프탈렌-2-아민, 1-브로모-4-클로로-2-아이오도벤젠 대신 1-브로모-2-아이오도벤젠을 사용하여 화학식 A의 제조 방법과 같은 방법으로 8-클로로-5H-벤조[b]카바졸을 합성했다.Bromo-2-iodobenzene instead of 7-chloronaphthalene-2-amine and 1-bromo-4-chloro-2-iodobenzene in place of naphthalene- 8-chloro-5H-benzo [b] carbazole was synthesized.
Figure PCTKR2018007083-appb-I000033
Figure PCTKR2018007083-appb-I000033
제조예 7. 화학식 G (7-클로로-5H-벤조[b]카바졸) 제조 Preparation 7. Preparation of the compound of formula G (7-chloro-5H-benzo [b] carbazole)
나프탈렌-2-아민 대신 8-클로로나프탈렌-2-아민, 1-브로모-4-클로로-2-아이오도벤젠 대신 1-브로모-2-아이오도벤젠을 사용하여 화학식 A의 제조 방법과 같은 방법으로 7-클로로-5H-벤조[b]카바졸을 합성했다.Bromo-2-iodobenzene instead of 8-chloronaphthalene-2-amine and 1-bromo-4-chloro-2-iodobenzene in place of naphthalene- 7-chloro-5H-benzo [b] carbazole was synthesized.
Figure PCTKR2018007083-appb-I000034
Figure PCTKR2018007083-appb-I000034
제조예 8. 화학식 H (6-클로로-5H-벤조[b]카바졸) 제조 Preparation 8. Preparation of the formula H (6-chloro-5H-benzo [b] carbazole)
나프탈렌-2-아민 대신 1-클로로나프탈렌-2-아민, 1-브로모-4-클로로-2-아이오도벤젠 대신 1-브로모-2-아이오도벤젠을 사용하여 화학식 A의 제조 방법과 같은 방법으로 6-클로로-5H-벤조[b]카바졸을 합성했다.Bromo-2-iodobenzene instead of 1-bromo-4-chloro-2-iodobenzene in place of 1-chloronaphthalene- 6-chloro-5H-benzo [b] carbazole was synthesized.
Figure PCTKR2018007083-appb-I000035
Figure PCTKR2018007083-appb-I000035
제조예 9. 화학식 I (11-클로로-5H-벤조[b]카바졸) 제조Preparation 9. Preparation of Formula I (11-chloro-5H-benzo [b] carbazole)
나프탈렌-2-아민 대신 4-클로로나프탈렌-2-아민, 1-브로모-4-클로로-2-아이오도벤젠 대신 1-브로모-2-아이오도벤젠을 사용하여 화학식 A의 제조 방법과 같은 방법으로 11-클로로-5H-벤조[b]카바졸을 합성했다.Bromo-2-iodobenzene instead of 4-chloronaphthalene-2-amine and 1-bromo-4-chloro-2-iodobenzene in place of naphthalene- To synthesize 11-chloro-5H-benzo [b] carbazole.
Figure PCTKR2018007083-appb-I000036
Figure PCTKR2018007083-appb-I000036
제조예 10. 화학식 I (10-클로로-5H-벤조[b]카바졸) 제조Preparation 10. Preparation of Formula I (10-chloro-5H-benzo [b] carbazole)
나프탈렌-2-아민 대신 5-클로로나프탈렌-2-아민, 1-브로모-4-클로로-2-아이오도벤젠 대신 1-브로모-2-아이오도벤젠을 사용하여 화학식 A의 제조 방법과 같은 방법으로 10-클로로-5H-벤조[b]카바졸을 합성했다.Bromo-2-iodobenzene instead of 5-chloronaphthalene-2-amine and 1-bromo-4-chloro-2-iodobenzene in place of naphthalene- To prepare 10-chloro-5H-benzo [b] carbazole.
Figure PCTKR2018007083-appb-I000037
Figure PCTKR2018007083-appb-I000037
상기 제조예 1 내지 10의 N에 결합된 수소는 본 발명의 -L1-Ar1으로, Cl은 -L2-Ar2로 Buchwald-Hartwig coupling reaction, Heck coupling reaction, Suzuki coupling reaction 의 방법을 이용하여 치환된다. The hydrogen bonded to N in the above Production Examples 1 to 10 is substituted with -L1-Ar1 of the present invention and Cl is replaced with -L2-Ar2 by the Buchwald-Hartwig coupling reaction, Heck coupling reaction, and Suzuki coupling reaction method.
또한, 본 명세서는 상기 전술한 화합물을 포함하는 유기 전계 발광 소자를 제공한다. The present invention also provides an organic electroluminescent device comprising the aforementioned compound.
본 출원의 일 실시상태에 있어서, 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자로서, 상기 유기물층 중 1 층 이상은 상기 화학식 1의 화합물을 포함하는 것인 유기 전계 발광 소자를 제공한다. In one embodiment of the present application, the first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers includes the compound of Formula 1 do.
본 명세서에서 어떤 부재가 다른 부재 "상에" 위치하고 있다고 할 때, 이는 어떤 부재가 다른 부재에 접해 있는 경우뿐 아니라 두 부재 사이에 또 다른 부재가 존재하는 경우도 포함한다.When a member is referred to herein as being " on " another member, it includes not only a member in contact with another member but also another member between the two members.
본 명세서에서 어떤 부분이 어떤 구성요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다. Whenever a component is referred to as " comprising ", it is to be understood that the component may include other components as well, without departing from the scope of the present invention.
본 출원의 유기 전계 발광 소자의 유기물층은 단층 구조로 이루어질 수도 있으나, 2층 이상의 유기물층이 적층된 다층 구조로 이루어질 수 있다. 예컨대, 본 발명의 유기 전계 발광 소자의 대표적인 예로서, 유기 전계 발광 소자는 유기물층으로서 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층 등을 포함하는 구조를 가질 수 있다. 그러나 유기 전계 발광 소자의 구조는 이에 한정되지 않고 더 적은 수의 유기층을 포함할 수 있다.The organic material layer of the organic electroluminescent device of the present application may have a single-layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, as a typical example of the organic electroluminescent device of the present invention, the organic electroluminescent device may have a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, etc. as an organic material layer. However, the structure of the organic electroluminescent device is not limited thereto and may include a smaller number of organic layers.
본 출원의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1의 화합물을 포함한다. In one embodiment of the present application, the organic layer includes a light-emitting layer, and the light-emitting layer includes the compound of the general formula (1).
본 출원의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1의 화합물을 포함하고, 상기 발광층은 적색 발광층이다.In one embodiment of the present application, the organic layer includes a light emitting layer, the light emitting layer includes the compound of Formula 1, and the light emitting layer is a red light emitting layer.
본 출원의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1의 화합물 호스트로 포함한다. In one embodiment of the present application, the organic layer includes a light emitting layer, and the light emitting layer includes a compound host of the formula (1).
본 출원의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1의 화합물 적색 호스트로 포함한다. In one embodiment of the present application, the organic layer includes a light emitting layer, and the light emitting layer includes the compound red host of the formula (1).
본 출원의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1의 화합물 및 도펀트를 포함한다. In one embodiment of the present application, the organic layer includes a light emitting layer, and the light emitting layer includes the compound of Formula 1 and a dopant.
본 출원의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1의 화합물 및 도펀트를 1:1 내지 100:1의 중량비로 포함한다. In one embodiment of the present application, the organic layer includes a light emitting layer, and the light emitting layer contains the compound of Formula 1 and the dopant in a weight ratio of 1: 1 to 100: 1.
본 출원의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 도펀트를 포함한다. In one embodiment of the present application, the organic layer includes a light emitting layer, and the light emitting layer includes a dopant.
본 출원의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 도펀트를 포함하고, 상기 도펀트는 금속착체이다. In one embodiment of the present application, the organic layer includes a light emitting layer, the light emitting layer includes a dopant, and the dopant is a metal complex.
본 출원의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 도펀트를 포함하고, 상기 도펀트는 이리듐계 금속착체이다. In one embodiment of the present application, the organic layer includes a light emitting layer, the light emitting layer includes a dopant, and the dopant is an iridium metal complex.
본 출원의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 도펀트는 하기 구조 중에서 선택될 수 있다. In one embodiment of the present application, the organic layer includes a light emitting layer, and the dopant of the light emitting layer may be selected from the following structures.
Figure PCTKR2018007083-appb-I000038
Figure PCTKR2018007083-appb-I000038
Figure PCTKR2018007083-appb-I000039
Figure PCTKR2018007083-appb-I000039
Figure PCTKR2018007083-appb-I000040
Figure PCTKR2018007083-appb-I000040
Figure PCTKR2018007083-appb-I000041
Figure PCTKR2018007083-appb-I000041
본 출원의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층의 두께는 100 Å 내지 700 Å이다. In one embodiment of the present application, the organic layer includes a light emitting layer, and the thickness of the light emitting layer is 100 to 700 ANGSTROM.
본 출원의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층의 두께는 300 Å 내지 500 Å이다. In one embodiment of the present application, the organic layer includes a light emitting layer, and the thickness of the light emitting layer is 300 ANGSTROM to 500 ANGSTROM.
본 출원의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층의 두께는 400 Å이다. In one embodiment of the present application, the organic layer includes a light emitting layer, and the thickness of the light emitting layer is 400 ANGSTROM.
본 출원의 일 실시상태에 있어서, 상기 유기물층은 정공주입층 또는 정공수송층을 포함하고, 상기 정공주입층 또는 정공수송층은 상기 화학식 1의 화합물을 포함한다. In one embodiment of the present application, the organic material layer includes a hole injecting layer or a hole transporting layer, and the hole injecting layer or the hole transporting layer includes the compound of the above formula (1).
본 출원의 일 실시상태에 있어서, 상기 유기물층은 정공주입층, 정공수송층 또는 정공 주입 및 수송층을 포함하고, 상기 정공주입층, 정공수송층 또는 정공 주입 및 수송층은 상기 화학식 1의 화합물을 포함한다. In one embodiment of the present application, the organic material layer includes a hole injecting layer, a hole transporting layer, or a hole injecting and transporting layer, and the hole injecting layer, the hole transporting layer, or the hole injecting and transporting layer includes the compound of Formula 1.
본 출원의 일 실시상태에 있어서, 상기 유기물층은 정공주입층을 포함하고, 상기 정공주입층은 도핑된다. In one embodiment of the present application, the organic layer includes a hole injection layer, and the hole injection layer is doped.
본 출원의 일 실시상태에 있어서, 상기 유기물층은 정공주입층을 포함하고, 상기 정공주입층은 p-도핑된다. In one embodiment of the present application, the organic layer includes a hole injection layer, and the hole injection layer is p-doped.
본 출원의 일 실시상태에 있어서, 상기 유기물층은 전자수송층 또는 전자주입층을 포함하고, 상기 전자수송층 또는 전자주입층은 상기 화학식 1의 화합물을 포함한다. In one embodiment of the present application, the organic layer includes an electron transporting layer or an electron injecting layer, and the electron transporting layer or the electron injecting layer includes the compound of the above formula (1).
본 출원의 일 실시상태에 있어서, 상기 유기물층은 전자주입층, 전자수송층 또는 전자 주입 및 수송층을 포함하고, 상기 전자주입층, 전자수송층 또는 전자 주입 및 수송층은 상기 화학식 1의 화합물을 포함한다. In one embodiment of the present application, the organic layer includes an electron injecting layer, an electron transporting layer, or an electron injecting and transporting layer, and the electron injecting layer, the electron transporting layer, or the electron injecting and transporting layer includes the compound of Formula 1.
본 출원의 일 실시상태에 있어서, 상기 유기물층은 전자 주입 및 수송층을 포함하고 상기 전자 주입 및 수송층은 리튬퀴놀레이트를 포함한다. In one embodiment of the present application, the organic layer comprises an electron injection and transport layer, and the electron injection and transport layer comprises lithium quinolate.
본 출원의 일 실시상태에 있어서, 상기 유기물층은 전자저지층 또는 정공저지층을 포함하고, 상기 전자저지층 또는 정공저지층은 상기 화학식 1의 화합물을 포함한다. In one embodiment of the present application, the organic layer includes an electron blocking layer or a hole blocking layer, and the electron blocking layer or the hole blocking layer includes the compound of the above formula (1).
본 출원의 일 실시상태에 있어서, 상기 유기 전계 발광 소자는 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 발광층; 상기 발광층과 상기 제1 전극 사이, 또는 상기 발광층과 상기 제2 전극 사이에 구비된 2층 이상의 유기물층을 포함하고, 상기 발광층은 상기 화학식 1의 화합물을 포함한다. In one embodiment of the present application, the organic electroluminescent device includes a first electrode; A second electrode facing the first electrode; And a light emitting layer provided between the first electrode and the second electrode; And at least two organic layers disposed between the light emitting layer and the first electrode or between the light emitting layer and the second electrode, wherein the light emitting layer comprises the compound of Formula 1.
본 출원의 일 실시상태에 있어서, 상기 2층 이상의 유기물층은 정공주입층, 정공수송층, 전자저지층, 정공저지층, 및 전자 주입 및 수송층으로 이루어진 군에서 2 이상 선택될 수 있다. In one embodiment of the present application, the two or more organic layers may be selected from the group consisting of a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, and an electron injecting and transporting layer.
또 하나의 실시상태에 있어서, 유기 전계 발광 소자는 기판 상에 양극, 1층 이상의 유기물층 및 음극이 순차적으로 적층된 구조(normal type)의 유기 발광 소자일 수 있다. In another embodiment, the organic electroluminescent device may be a normal type organic light emitting device in which an anode, at least one organic layer, and a cathode are sequentially stacked on a substrate.
또 하나의 실시상태에 있어서, 유기 전계 발광 소자는 기판 상에 음극, 1층 이상의 유기물층 및 양극이 순차적으로 적층된 역방향 구조(inverted type)의 유기 발광 소자일 수 있다. In another embodiment, the organic electroluminescent device may be an inverted type organic light emitting device in which a cathode, at least one organic layer, and an anode are sequentially stacked on a substrate.
예컨대, 본 출원의 일 실시상태에 따른 유기 전계 발광 소자의 구조는 도 1 및 2에 예시되어 있다. For example, the structure of an organic electroluminescent device according to one embodiment of the present application is illustrated in Figs. 1 and 2. Fig.
도 1은 기판(1), 양극(2), 발광층(3), 음극(4)이 순차적으로 적층된 유기 전계 발광 소자의 구조가 예시되어 있다. 이와 같은 구조에 있어서, 상기 화합물은 상기 발광층(3)에 포함될 수 있다. 1 shows a structure of an organic electroluminescent device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially laminated. In such a structure, the compound may be included in the light emitting layer (3).
도 2는 기판 (1), 양극(2), 정공주입층(5), 정공수송층(6), 전자저지층(7), 발광층(3), 정공저지층(8), 전자 주입 및 수송층(9) 및 음극(4)이 순차적으로 적층된 유기 전계 발광 소자의 구조가 예시되어 있다. 이와 같은 구조에 있어서 상기 화합물은 상기 발광층(3) 에 포함될 수 있다. Fig. 2 is a cross-sectional view showing the structure of a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, an electron blocking layer 7, a light emitting layer 3, a hole blocking layer 8, 9, and a cathode 4 are sequentially laminated on a transparent substrate 1, as shown in FIG. In such a structure, the compound may be included in the light-emitting layer (3).
이와 같은 구조에 있어서, 상기 화합물은 상기 정공주입층, 정공수송층, 발광층 및 전자수송층 중 1층 이상에 포함될 수 있다. In such a structure, the compound may be contained in at least one of the hole injecting layer, the hole transporting layer, the light emitting layer, and the electron transporting layer.
본 출원의 유기 전계 발광 소자는 유기물층 중 1층 이상이 본 출원의 화합물, 즉 상기 화합물을 포함하는 것을 제외하고는 당 기술분야에 알려져 있는 재료와 방법으로 제조될 수 있다.The organic electroluminescent device of the present application can be produced by materials and methods known in the art, except that one or more of the organic layers include the compound of the present application, i.e., the compound.
상기 유기 발광 소자가 복수개의 유기물층을 포함하는 경우, 상기 유기물층은 동일한 물질 또는 다른 물질로 형성될 수 있다. When the organic light emitting diode includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.
예컨대, 본 출원의 유기 발광 소자는 기판 상에 제1 전극, 유기물층 및 제2 전극을 순차적으로 적층시킴으로써 제조할 수 있다. 이 때 스퍼터링법(sputtering)이나 전자빔 증발법(e-beam evaporation)과 같은 PVD(physical Vapor Deposition)방법을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공 주입층, 정공 수송층, 발광층 및 전자 수송층을 포함하는 유기물층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다. 이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 만들 수 있다. For example, the organic light emitting device of the present application can be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as a sputtering method or an e-beam evaporation method, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate to form a positive electrode Forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer and an electron transporting layer thereon, and depositing a material usable as a cathode thereon. In addition to such a method, an organic light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.
또한, 상기 화학식 1의 화합물은 유기 전계 발광 소자의 제조시 진공 증착법 뿐만 아니라 용액 도포법에 의하여 유기물층으로 형성될 수 있다. 여기서, 용액 도포법이라 함은 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯프린팅, 스크린 프린팅, 스프레이법, 롤 코팅 등을 의미하지만, 이들만으로 한정되는 것은 아니다.In addition, the compound of Formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum evaporation method in the production of an organic electroluminescent device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating and the like, but is not limited thereto.
이와 같은 방법 외에도, 기판 상에 음극 물질로부터 유기물층, 양극 물질을 차례로 증착시켜 유기 전계 발광 소자를 만들 수도 있다 (국제 특허 출원 공개 제 2003/012890호). 다만, 제조 방법이 이에 한정되는 것은 아니다. In addition to such a method, an organic electroluminescent device can also be fabricated by sequentially depositing an organic material layer and a cathode material on a substrate from a cathode material (International Patent Application Publication No. 2003/012890). However, the manufacturing method is not limited thereto.
본 출원의 일 실시상태에 있어서, 상기 제1 전극은 양극이고, 상기 제2 전극은 음극이다. In one embodiment of the present application, the first electrode is an anode and the second electrode is a cathode.
또 하나의 실시상태에 있어서, 상기 제1 전극은 음극이고, 상기 제2 전극은 양극이다. In another embodiment, the first electrode is a cathode and the second electrode is a cathode.
상기 양극 물질로는 통상 유기물층으로 정공 주입이 원활할 수 있도록 일함수가 큰 물질이 바람직하다. 본 발명에서 사용될 수 있는 양극 물질의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연 산화물, 인듐 산화물, 인듐주석 산화물(ITO), 인듐아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2 : Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDOT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다. As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO 2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.
상기 음극 물질로는 통상 유기물층으로 전자 주입이 용이하도록 일함수가 작은 물질인 것이 바람직하다. 음극 물질의 구체적인 예로는 마그네슘, 칼슘, 나트륨, 칼륨, 티타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석 및 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다. The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as LiF / Al or LiO 2 / Al, but are not limited thereto.
상기 정공 주입층은 전극으로부터 정공을 주입하는 층으로, 정공 주입 물질로는 정공을 수송하는 능력을 가져 양극에서의 정공 주입효과, 발광층 또는 발광재료에 대하여 우수한 정공 주입 효과를 갖고, 발광층에서 생성된 여기자의 전자주입층 또는 전자주입재료에의 이동을 방지하며, 또한, 박막 형성 능력이 우수한 화합물이 바람직하다. 정공 주입 물질의 HOMO(highest occupied molecular orbital)가 양극 물질의 일함수와 주변 유기물층의 HOMO 사이인 것이 바람직하다. 정공 주입 물질의 구체적인 예로는 금속 포피린(porphyrin), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴헥사아자트리페닐렌 계열의 유기물, 퀴나크리돈(quinacridone)계열의 유기물, 페릴렌(perylene) 계열의 유기물, 안트라퀴논 및 폴리아닐린과 폴리티오펜 계열의 전도성 고분자 등이 있으나, 이들에만 한정 되는 것은 아니다. The hole injecting layer is a layer for injecting holes from an electrode. The hole injecting material has a hole injecting effect, and has a hole injecting effect on the light emitting layer or a light emitting material. A compound which prevents the migration of excitons to the electron injecting layer or the electron injecting material and is also excellent in the thin film forming ability is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.
상기 정공수송층은 정공주입층으로부터 정공을 수취하여 발광층까지 정공을 수송하는 층으로, 정공 수송 물질로는 양극이나 정공 주입층으로부터 정공을 수송받아 발광층으로 옮겨줄 수 있는 물질로 정공에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 아릴아민 계열의 유기물, 전도성 고분자, 및 공액 부분과 비공액 부분이 함께 있는 블록 공중합체 등이 있으나, 이들에만 한정되는 것은 아니다. The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer. The hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer. The material is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.
상기 발광 물질로는 정공 수송층과 전자 수송층으로부터 정공과 전자를 각각 수송받아 결합시킴으로써 가시광선 영역의 빛을 낼 수 있는 물질로서, 형광이나 인광에 대한 양자 효율이 좋은 물질이 바람직하다. 구체적인 예로는 8-히드록시-퀴놀린 알루미늄 착물(Alq3); 카르바졸 계열 화합물; 이량체화 스티릴(dimerized styryl) 화합물; BAlq; 10-히드록시벤조 퀴놀린-금속 화합물; 벤족사졸, 벤즈티아졸 및 벤즈이미다졸 계열의 화합물; 폴리(p-페닐렌비닐렌)(PPV) 계열의 고분자; 스피로(spiro) 화합물; 폴리플루오렌, 루브렌 등이 있으나, 이들에만 한정되는 것은 아니다. The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq 3 ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.
상기 발광층은 호스트 재료 및 도펀트 재료를 포함할 수 있다. 호스트 재료는 축합 방향족환 유도체 또는 헤테로환 함유 화합물 등이 있다. 구체적으로 축합 방향족환 유도체로는 안트라센 유도체, 피렌 유도체, 나프탈렌 유도체, 펜타센 유도체, 페난트렌 화합물, 플루오란텐 화합물 등이 있고, 헤테로환 함유 화합물로는 화합물, 디벤조퓨란 유도체, 래더형 퓨란 화합물, 피리미딘 유도체 등이 있으나, 이에 한정되지 않는다. The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic compound. Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds. Examples of heterocycle-containing compounds include compounds, dibenzofuran derivatives, ladder furan compounds , Pyrimidine derivatives, and the like, but are not limited thereto.
상기 전자 수송 물질로는 전자주입층으로부터 전자를 수취하여 발광층까지 전자를 수송하는 층으로 전자 수송 물질로는 음극으로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 물질로서, 전자에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 8-히드록시퀴놀린의 Al착물; Alq3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다. 전자 수송층은 종래기술에 따라 사용된 바와 같이 임의의 원하는 캐소드 물질과 함께 사용할 수 있다. 특히, 적절한 캐소드 물질의 예는 낮은 일함수를 가지고 알루미늄층 또는 실버층이 뒤따르는 통상적인 물질이다. 구체적으로 세슘, 바륨, 칼슘, 이테르븀 및 사마륨이고, 각 경우 알루미늄 층 또는 실버층이 뒤따른다.The electron transporting material is a layer that receives electrons from the electron injecting layer and transports electrons to the light emitting layer. The electron transporting material is a material capable of transferring electrons from the cathode well to the light emitting layer. Is suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transporting layer can be used with any desired cathode material as used according to the prior art. In particular, an example of a suitable cathode material is a conventional material having a low work function followed by an aluminum layer or a silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.
상기 전자주입층은 전극으로부터 전자를 주입하는 층으로, 전자를 수송하는 능력을 갖고, 음극으로부터의 전자주입 효과, 발광층 또는 발광 재료에 대하여 우수한 전자주입 효과를 가지며, 발광층에서 생성된 여기자의 정공 주입층에의 이동을 방지하고, 또한, 박막형성능력이 우수한 화합물이 바람직하다. 구체적으로는 플루오레논, 안트라퀴노다이메탄, 다이페노퀴논, 티오피란 다이옥사이드, 옥사졸, 옥사다이아졸, 트리아졸, 이미다졸, 페릴렌테트라카복실산, 프레오레닐리덴 메탄, 안트론 등과 그들의 유도체, 금속 착체 화합물 및 함질소 5원환 유도체 등이 있으나, 이에 한정되지 않는다. The electron injection layer is a layer for injecting electrons from the electrode. The electron injection layer has an ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron injection effect with respect to the light emitting layer or the light emitting material. A compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A complex compound and a nitrogen-containing five-membered ring derivative, but are not limited thereto.
상기 금속 착체 화합물로서는 8-하이드록시퀴놀리나토 리튬, 비스(8-하이드록시퀴놀리나토)아연, 비스(8-하이드록시퀴놀리나토)구리, 비스(8-하이드록시퀴놀리나토)망간, 트리스(8-하이드록시퀴놀리나토)알루미늄, 트리스(2-메틸-8-하이드록시퀴놀리나토)알루미늄, 트리스(8-하이드록시퀴놀리나토)갈륨, 비스(10-하이드록시벤조[h]퀴놀리나토)베릴륨, 비스(10-하이드록시벤조[h]퀴놀리나토)아연, 비스(2-메틸-8-퀴놀리나토)클로로갈륨, 비스(2-메틸-8-퀴놀리나토)(o-크레졸라토)갈륨, 비스(2-메틸-8-퀴놀리나토)(1-나프톨라토)알루미늄, 비스(2-메틸-8-퀴놀리나토)(2-나프톨라토)갈륨 등이 있으나, 이에 한정되지 않는다.Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.
상기 정공저지층은 정공의 음극 도달을 저지하는 층으로, 일반적으로 정공주입층과 동일한 조건으로 형성될 수 있다. 구체적으로 옥사디아졸 유도체나 트리아졸 유도체, 페난트롤린 유도체, BCP, 알루미늄 착물 (aluminum complex) 등이 있으나, 이에 한정되지 않는다. The hole blocking layer prevents holes from reaching the cathode, and may be formed under the same conditions as those of the hole injecting layer. Specific examples thereof include, but are not limited to, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes and the like.
본 명세서에 따른 유기 전계 발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic electroluminescent device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.
상기 화학식 1로 표시되는 화합물 및 이를 포함하는 유기 전계 발광 소자의 제조는 이하 실시예에서 구체적으로 설명한다. 그러나 하기 실시예는 본 명세서를 예시하기 위한 것이며, 본 명세서의 범위가 이들에 의하여 한정되는 것은 아니다.The preparation of the compound represented by Formula 1 and the organic electroluminescent device including the same will be described in detail in the following examples. However, the following examples are intended to illustrate the present specification, and the scope of the present specification is not limited thereto.
<< 합성예Synthetic example >>
합성예Synthetic example 1 One
Figure PCTKR2018007083-appb-I000042
Figure PCTKR2018007083-appb-I000042
화학식 B 10.0 g (1.0 eq), 2-클로로-4-(나프탈렌-2-일)퀴나졸린 12.71 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 1-9-a 12.26 g (수율 61 %)을 얻었다. [M+H]=507Formula B 10.0 g (1.0 eq), 2- chloro-4- (naphthalen-2-yl) quinazoline 12.71 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq), Pd (t-Bu 3 P) 2 0.05 g (0.002 eq) was dissolved in 250 ml of xylene, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 12.26 g (yield: 61%) of the compound 1-9-a. [M + H] &lt; + &gt; = 507
화학식 1-9-a 12.26 g (1.0 eq), 디벤조[b,d]퓨란-4-일보론산 5.65 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.29 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 1-9 10.45 g (수율 67 %)를 얻었다. [M+H]=638Formula 1-9-a 12.26 g (1.0 eq ), dibenzo [b, d] furan-4-Daily acid 5.65 g (1.1 eq), Pd (t-Bu 3 P) 2 0.13 g (0.01 eq) of dioxane , And 10.29 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added, and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 10.45 g (yield 67%) of Compound 1-9. [M + H] &lt; / RTI &gt; = 638
합성예 2Synthesis Example 2
Figure PCTKR2018007083-appb-I000043
Figure PCTKR2018007083-appb-I000043
화학식 C 10.0 g (1.0 eq), 2-클로로-4-(4-(페난트렌-9-일)페닐)퀴나졸린 18.22 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 1-16-a 15.81 g (수율 63 %)을 얻었다. [M+H]=633Formula C 10.0 g (1.0 eq), 2- chloro-4- (4- (phenanthrene-9-yl) phenyl) quinazoline 18.22 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq), Pd ( 0.05 g (0.002 eq) of t-Bu 3 P) 2 was dissolved in 250 ml of xylene and refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 15.81 g (yield: 63%) of the compound 1-16-a. [M + H] &lt; + &gt; = 633
화학식 1-16-a 15.81 g (1.0 eq), (2-(디벤조[b,d]티오펜-2-일_페닐)보론산 8.37 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.62 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 1-16 16.21 g (수율 75 %)를 얻었다. [M+H]=8578.37 g (1.1 eq) of Pd (t-Bu 3 P), 15.81 g (1.0 eq) of the compound of the formula 1-16-a, 2- (dibenzo [b, d] thiophen- 2 was dissolved in 250 ml of dioxane, and 10.62 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added thereto, followed by refluxing and stirring. After completion of the reaction for 2 hours, the water layer containing the salt was removed, After removing the solvent, the solution was completely dissolved in chloroform, washed with water, and then decompressed to remove about 50% of the solvent, and then ethyl acetate was added thereto under reflux, and the crystals were dropped, cooled and filtered. -16 16.21 g (yield 75%). [M + H] = 857
합성예 3Synthesis Example 3
Figure PCTKR2018007083-appb-I000044
Figure PCTKR2018007083-appb-I000044
화학식 A 10.0 g (1.0 eq), 2-클로로-4-(디벤조[b,d]퓨란-3-일)퀴나졸린 14.46 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 1-30-a 13.84 g (수율 64 %)을 얻었다. [M+H]=547Formula A 10.0 g (1.0 eq), 2- chloro-4- (dibenzo [b, d] furan-3-yl) quinazoline 14.46 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq), Pd 0.05 g (0.002 eq) of (t-Bu 3 P) 2 was dissolved in 250 ml of xylene, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 13.84 g (yield 64%) of the compound 1-30-a. [M + H] &lt; + &gt; = 547
화학식 1-30-a 13.84 g (1.0 eq), 디벤조[b,d]퓨란-3-일보론산.91 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.76 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 1-30 11.84 g (수율 69 %)를 얻었다. 화학식 1-30의 질량 분석 스펙트럼을 도 5에 나타내었다. [M+H]=678The compound of Formula 1-30-a 13.84 g (1.0 eq ), dibenzo [b, d] furan-3 acid daily .91 g (1.1 eq), Pd (t-Bu 3 P) 2 0.13 g (0.01 eq) Dioxane, and 10.76 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 11.84 g (yield 69%) of Compound 1-30. The mass spectrometry spectrum of the compound of Formula 1-30 is shown in Fig. [M + H] = 678
합성예 4Synthesis Example 4
Figure PCTKR2018007083-appb-I000045
Figure PCTKR2018007083-appb-I000045
화학식 E 10.0 g (1.0 eq), 3-(2-클로로퀴나졸린-4-일)-11-페닐-11H-벤조[a]카바졸 19.93 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 1-44-a 17.21 g (수율 64 %)을 얻었다. [M+H]=67211.9 g (1.1 eq) of K 3 PO 4, 16.86 g (2.0 eq) of 3- (2-chloroquinazolin-4-yl) eq) and 0.05 g (0.002 eq) of Pd (t-Bu 3 P) 2 were dissolved in 250 ml of xylene, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 17.21 g (yield: 64%) of the compound 1-44-a. [M + H] = 672
화학식 1-44-a 17.21 g (1.0 eq), (2-(디벤조[b,d]퓨란-3-일)페닐)보론산 8.13 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.88 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 1-44 14.25 g (수율 63 %)를 얻었다. [M+H]=8808.13 g (1.1 eq) of Pd (t-BuP 3 ) 2 (dibenzo [b, d] furan- 0.13 g (0.01 eq) was added to 250 ml of dioxane, and 10.88 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 14.25 g (yield: 63%) of Compound 1-44. [M + H] &lt; + &gt; = 880
합성예 5Synthesis Example 5
Figure PCTKR2018007083-appb-I000046
Figure PCTKR2018007083-appb-I000046
화학식 G 10.0 g (1.0 eq), 2-클로로-4-(4-(퀴놀린-8-일)페닐)퀴나졸린 16.08 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 1-59-a 15.34 g (수율 66 %)을 얻었다. [M+H]=584Formula G 10.0 g (1.0 eq), 2- chloro-4- (4- (quinolin-8-yl) phenyl) quinazoline 16.08 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq), Pd (t -Bu 3 P) 2 (0.05 g, 0.002 eq) was dissolved in 250 ml of xylene, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 15.34 g (yield 66%) of a compound 1-59-a. [M + H] = 584
화학식 1-59-a 15.34 g (1.0 eq), 디벤조[b,d]티오펜-3-일보론산 6.60 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 11.17 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 1-59 13.82 g (수율 72 %)를 얻었다. [M+H]=731Formula for 1-59-a 15.34 g (1.0 eq ), dibenzo [b, d] thiophene-3 Daily acid 6.60 g (1.1 eq), Pd (t-Bu 3 P) 2 0.13 g (0.01 eq) (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added to the solution, and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 13.82 g (yield 72%) of Compound 1-59. [M + H] = 731
합성예 6Synthesis Example 6
Figure PCTKR2018007083-appb-I000047
Figure PCTKR2018007083-appb-I000047
화학식 A 10.0 g (1.0 eq), 2-클로로-4-(나프탈렌-1-일)-6-페닐퀴나졸린 16.03 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 1-68-a 14.87 g (수율 64 %)을 얻었다. [M+H]=583Formula A 10.0 g (1.0 eq), 2- chloro-4- (naphthalene-1-yl) -6-phenyl-quinazoline 16.03 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq), Pd (t- Bu 3 P) 2 0.05 g (0.002 eq) was dissolved in 250 ml of xylene, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 14.87 g (yield 64%) of the compound 1-68-a. [M + H] = 583
화학식 1-68-a 14.87 g (1.0 eq), (4-(디벤조[b,d]티오펜-1-일)페닐)보론산 8.55 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.84 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 1-68 14.22 g (수율 69 %)를 얻었다. [M+H]=8078.55 g (1.1 eq) of Pd (t-Bu 3 P), 14.87 g (1.0 eq) of formula 1-68-a, 2 was dissolved in 250 ml of dioxane, and 10.84 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added, and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 14.22 g (yield 69%) of Compound 1-68. [M + H] &lt; + &gt; = 807
합성예 7Synthesis Example 7
Figure PCTKR2018007083-appb-I000048
Figure PCTKR2018007083-appb-I000048
화학식 I 10.0 g (1.0 eq), 6-([1,1'-비페닐]-3-일)-2-(4-브로모나프탈렌-1-일)-4-(디벤조[b,d]퓨란-2-일)퀴나졸린 28.56 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 1-89-a 20.44 g (수율 62 %)을 얻었다. [M+H]=82510.0 g (1.0 eq) of the compound of the formula I, 6 - ([1,1'-biphenyl] -3-yl) -2- (4-bromonaphthalen- ] furan-2-yl) quinazoline 28.56 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq), a Pd (t-Bu 3 P) 2 0.05 g (0.002 eq) and xylene (xylene) 250 ml And the mixture was refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 20.44 g (yield 62%) of the compound 1-89-a. [M + H] = 825
화학식 1-89-a 20.44 g (1.0 eq), 디벤조[b,d]티오펜-3-일보론산 6.22 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.52 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 1-89 17.47 g (수율 72 %)를 얻었다. [M+H]=973Formula for 1-89-a 20.44 g (1.0 eq ), dibenzo [b, d] thiophene-3 Daily acid 6.22 g (1.1 eq), Pd (t-Bu 3 P) 2 0.13 g (0.01 eq) 10.52 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added to 250 ml of dioxane, and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 17.47 g (yield 72%) of Compound 1-89. [M + H] &lt; + &gt; = 973
합성예 8Synthesis Example 8
Figure PCTKR2018007083-appb-I000049
Figure PCTKR2018007083-appb-I000049
화학식 J 10.0 g (1.0 eq), 2-(4-브로모나프탈렌-2-일)-4-(디벤조[b,d]티오펜-4-일)-6-(나프탈렌-1-일)퀴나졸린 28.13 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 1-95-a 21.42 g (수율 66 %)을 얻었다. [M+H]=815(Dibenzo [b, d] thiophen-4-yl) -6- (naphthalen-1-yl) quinazoline was stirred and 28.13 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq), reflux dissolving Pd (t-Bu 3 P) 2 0.05 g (0.002 eq) in 250 ml of xylene (xylene). When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 21.42 g (yield: 66%) of the compound 1-95-a. [M + H] &lt; + &gt; = 815
화학식 1-95-a 21.42 g (1.0 eq), 디벤조[b,d]퓨란-2-일보론산 6.14 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 11.17 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 1-95 15.48 g (수율 62 %)를 얻었다. [M+H]=947The compound of Formula 1-95-a 21.42 g (1.0 eq ), dibenzo [b, d] furan-2-Daily acid 6.14 g (1.1 eq), Pd (t-Bu 3 P) 2 0.13 g (0.01 eq) in dioxane , And 11.17 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added thereto, followed by reflux and stirring. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 15.48 g (yield 62%) of Compound 1-95. [M + H] &lt; + &gt; = 947
합성예 9Synthesis Example 9
Figure PCTKR2018007083-appb-I000050
Figure PCTKR2018007083-appb-I000050
화학식 G 10.0 g (1.0 eq), 2-(2-클로로-6-페닐퀴나졸린-4-일)-5-페닐-5H-벤조[b]카바졸 23.25 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 1-107-a 19.28 g (수율 65 %)을 얻었다. [M+H]=748, 23.25 g (1.1 eq) of K 2 PO 4 (1 eq), 10.0 g (1.0 eq) of 2- (2- And 0.05 g (0.002 eq) of Pd (t-Bu 3 P) 2 were dissolved in 250 ml of xylene, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 19.28 g (yield: 65%) of Compound 1-107-a. [M + H] &lt; + &gt; = 748
화학식 1-107-a 19.28 g (1.0 eq), 디벤조[b,d]티오펜-1-일보론산 6.47 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.95 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 1-107 16.13 g (수율 70 %)를 얻었다. [M+H]=896Formula 1-107-a 19.28 g (1.0 eq ), dibenzo [b, d] thiophene-1-Daily acid 6.47 g (1.1 eq), Pd (t-Bu 3 P) 2 0.13 g (0.01 eq) of Dioxane, and 10.95 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added, and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 16.13 g (yield 70%) of Compound 1-107. [M + H] &lt; / RTI &gt; = 896
합성예 10Synthesis Example 10
Figure PCTKR2018007083-appb-I000051
Figure PCTKR2018007083-appb-I000051
화학식 B 10.0 g (1.0 eq), 2-([1,1':3',1''-터페닐]-5'-일)-4-클로로퀴나졸린 17.17 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 2-7-a 15.24 g (수율 63 %)을 얻었다. [M+H]=60917.17 g (1.1 eq) of K 2 PO 4 (1.0 eq), 2 - ([1,1 ': 3', 1 '' - terphenyl] 4 16.86 g (2.0 eq) of Pd (t-Bu 3 P) 2 and 0.05 g (0.002 eq) of Pd were dissolved in 250 ml of xylene and refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 15.24 g (yield: 63%) of the compound 2-7-a. [M + H] = 609
화학식 2-7-a 15.24 g (1.0 eq), (3-(디벤조[b,d]티오펜-3-일)페닐)보론산 8.38 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.64 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 2-7 13.64 g (수율 65 %)를 얻었다. [M+H]=8338.38 g (1.1 eq) of Pd (t-Bu 3 P), 15.24 g (1.0 eq) of the compound 2-7-a, 8.38 g (3- dibenzo [b, d] thiophen- 2 (0.1 eq.) Was placed in 250 ml of dioxane, and 10.64 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 13.64 g (yield 65%) of Compound 2-7. [M + H] = 833
합성예 11Synthesis Example 11
Figure PCTKR2018007083-appb-I000052
Figure PCTKR2018007083-appb-I000052
화학식 D 10.0 g (1.0 eq), 4-클로로-2-(9,9-디메틸-9H-플루오렌-4-일)퀴나졸린 15.59 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 2-21-a 14.76 g (수율 65 %)을 얻었다. [M+H]=573Formula D 10.0 g (1.0 eq), 4- chloro-2- (9,9-dimethyl -9H- fluorene-4-yl) quinazoline 15.59 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq) And 0.05 g (0.002 eq) of Pd (t-Bu 3 P) 2 were dissolved in 250 ml of xylene, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 14.76 g (yield 65%) of the compound 2-21-a. [M + H] &lt; + &gt; = 573
화학식 2-21-a 14.76 g (1.0 eq), (3-(디벤조[b,d]퓨란-4-일)페닐)보론산 8.18 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.95 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 2-21 12.94 g (수율 64 %)를 얻었다. [M+H]=7818.1 e g (1.1 eq) of Pd (t-Bu 3 P) 2 (1 eq), 14.76 g (1.0 eq) of 2- 0.13 g (0.01 eq) of the compound was dissolved in 250 ml of dioxane, and 10.95 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added thereto, followed by reflux and stirring. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 12.94 g (yield 64%) of Compound 2-21. [M + H] = 781
합성예 12Synthesis Example 12
Figure PCTKR2018007083-appb-I000053
Figure PCTKR2018007083-appb-I000053
화학식 A 10.0 g (1.0 eq), 4-클로로-2-(디벤조[b,d]퓨란-1-일)퀴나졸린 14.46 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 2-28-a 13.25 g (수율 65 %)을 얻었다. [M+H]=547Formula A 10.0 g (1.0 eq), 4- chloro-2- (dibenzo [b, d] furan-1-yl) quinazoline 14.46 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq), Pd 0.05 g (0.002 eq) of (t-Bu 3 P) 2 was dissolved in 250 ml of xylene, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 13.25 g (yield 65%) of the compound 2-28-a. [M + H] &lt; + &gt; = 547
화학식 2-28-a 13.25 g (1.0 eq), (디벤조[b,d]티오펜-1-일보론산 6.09 g (1.1 eq), Pd(t-Bu3P)2 0.12 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.30 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 2-28 12.1 g (수율 72 %)를 얻었다. [M+H]=695Formula 2-28-a 13.25 g (1.0 eq ), ( dibenzo [b, d] thiophene-1-Daily acid 6.09 g (1.1 eq), Pd (t-Bu 3 P) 2 0.12 g (0.01 eq) 10.30 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added, and the mixture was refluxed and stirred. After completion of the reaction for 2 hours, the water layer containing the salt was removed and the solvent was removed under reduced pressure. The crystals were filtered off by adding ethyl acetate to the filtrate under reflux, and the filtrate was subjected to column chromatography to obtain 12.1 g of Compound 2-28 (yield 72%). %). [M + H] = 695
합성예 13Synthesis Example 13
Figure PCTKR2018007083-appb-I000054
Figure PCTKR2018007083-appb-I000054
화학식 I 10.0 g (1.0 eq), 3-(4-클로로퀴나졸린-2-일)-7-페닐-7H-벤조[c]카바졸 19.93 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 2-53-a 18.92 g (수율 71 %)을 얻었다. [M+H]=67219.93 g (1.1 eq) of K 3 PO 4, 16.86 g (2.0 eq.) Of K 3 PO 4 , 10.0 g (1.0 eq) of 3- eq) and 0.05 g (0.002 eq) of Pd (t-Bu 3 P) 2 were dissolved in 250 ml of xylene, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 18.92 g (yield: 71%) of the compound 2-53-a. [M + H] = 672
화학식 2-53-a 18.92 g (1.0 eq), 디벤조[b,d]티오펜-4-일보론산 7.07 g (1.1 eq), Pd(t-Bu3P)2 0.14 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 11.97 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 2-53 16.54 g (수율 72 %)를 얻었다. [M+H]=820Formula for 2-53-a 18.92 g (1.0 eq ), dibenzo [b, d] thiophene-4 Daily acid 7.07 g (1.1 eq), Pd (t-Bu 3 P) 2 0.14 g (0.01 eq) (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added, and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 16.54 g (yield 72%) of Compound 2-53. [M + H] = 820
합성예 14Synthesis Example 14
Figure PCTKR2018007083-appb-I000055
Figure PCTKR2018007083-appb-I000055
화학식 J 10.0 g (1.0 eq), 2-([1,1'-비페닐]-3-일)-4-(4-브로모페닐)-7-(나프탈렌-2-일)퀴나졸린 24.63 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 2-64-a 17.96 g (수율 62 %)을 얻었다. [M+H]=73524.63 g of the compound represented by the formula J (1.0 eq) and 2 - ([1,1'-biphenyl] -3-yl) -4- (4-bromophenyl) -7- (naphthalen-2-yl) quinazoline (1.1 eq), 16.86 g (2.0 eq) of K 3 PO 4 and 0.05 g (0.002 eq) of Pd (t-Bu 3 P) 2 were dissolved in 250 ml of xylene and refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 17.96 g (yield: 62%) of the compound 2-64-a. [M + H] = 735
화학식 2-64-a 17.96 g (1.0 eq), 디벤조[b,d]퓨란-3-일보론산 5.70 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.38 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 2-64 14.58 g (수율 69 %)를 얻었다. [M+H]=867The compound of Formula 2-64-a 17.96 g (1.0 eq ), dibenzo [b, d] furan-3-Daily acid 5.70 g (1.1 eq), Pd (t-Bu 3 P) 2 0.13 g (0.01 eq) in dioxane , And 10.38 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added, and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 14.58 g (yield 69%) of the compound 2-64. [M + H] = 867
합성예 15Synthesis Example 15
Figure PCTKR2018007083-appb-I000056
Figure PCTKR2018007083-appb-I000056
화학식 E 10.0 g (1.0 eq), 4-(4-브로모페닐)-2-(4-(페난트렌-9-일)페닐)-7-페닐퀴나졸린 26.81 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 2-76-a 19.74 g (수율 63 %)을 얻었다. [M+H]=785Formula E 10.0 g (1.0 eq), 4- (4- Bromo-phenyl) -2- (4- (phenanthrene-9-yl) phenyl) -7-phenyl-quinazoline 26.81 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq) of Pd (t-Bu 3 P) 2 and 0.05 g (0.002 eq) of Pd were dissolved in 250 ml of xylene and refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 19.74 g (yield: 63%) of the compound 2-76-a. [M + H] = 785
화학식 2-76-a 17.96 g (1.0 eq), 디벤조[b,d]팅펜-2-일보론산 6.31 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.68 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 2-76 14.65 g (수율 62 %)를 얻었다. [M+H]=933The compound of Formula 2-76-a 17.96 g (1.0 eq ), dibenzo [b, d] Daily 2-tingpen acid 6.31 g (1.1 eq), Pd (t-Bu 3 P) 2 0.13 g (0.01 eq) in dioxane And then 10.68 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added, and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 14.65 g (yield 62%) of the compound 2-76. [M + H] &lt; + &gt; = 933
합성예 16Synthesis Example 16
Figure PCTKR2018007083-appb-I000057
Figure PCTKR2018007083-appb-I000057
화학식 F 10.0 g (1.0 eq), 4-(4-브로모나프탈렌-1-일)-2-(9,9-디메틸-9H-플루오렌-2-일)-7-(피리딘-3-일)퀴나졸린 26.42 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 2-79-a 18.96 g (수율 62 %)을 얻었다. [M+H]=776(10 g, 1.0 eq), 4- (4-bromonaphthalen-1-yl) -2- (9,9-dimethyl- ) the quinazoline 26.42 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq), Pd (t-Bu 3 P) 2 0.05 g (0.002 eq) were stirred under reflux dissolved in 250 ml of xylene (xylene) . When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 18.96 g (yield: 62%) of the compound 2-79-a. [M + H] = 776
화학식 2-79-a 18.96 g (1.0 eq), dibenzo[b,d]furan-1-ylboronic acid 5.70 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.38 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 2-79 13.68 g (수율 62 %)를 얻었다. [M+H]=908Formula 2-79-a 18.96 g (1.0 eq ), dibenzo [b, d] furan-1-ylboronic acid 5.70 g (1.1 eq), Pd (t-Bu 3 P) 2 0.13 g (0.01 eq) in dioxane to 250ml a mixture was stirred under reflux by placing a K 3 PO 4 10.38 g (2.0 eq) was dissolved in 80ml water. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 13.68 g (yield: 62%) of Compound 2-79. [M + H] &lt; + &gt; = 908
합성예 17Synthesis Example 17
Figure PCTKR2018007083-appb-I000058
Figure PCTKR2018007083-appb-I000058
화학식 H 10.0 g (1.0 eq), 2-(4-클로로-6-(나프탈렌-2-일)퀴나졸린-2-일)-9-페닐-9H-카바졸 23.25 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 2-96-a 19.24 g (수율 65 %)을 얻었다. [M+H]=74823.25 g (1.1 eq) of K ( 3 eq.), 10.0 g (1.0 eq) of the compound of formula (II), 2- (4-chloro-6- (naphthalen-2-yl) quinazolin- (2.0 eq) of PO 4 and 0.05 g (0.002 eq) of Pd (t-Bu 3 P) 2 were dissolved in 250 ml of xylene and refluxed with stirring. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 19.24 g (yield 65%) of the compound 2-96-a. [M + H] &lt; + &gt; = 748
화학식 2-96-a 19.24 g (1.0 eq), 디벤조[b,d]티오펜-2-일보론산 6.46 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.93 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 2-96 16.59 g (수율 72 %)를 얻었다. 화학식 2-96의 질량 분석 스펙트럼을 도 6에 나타내었다. [M+H]=896Formula for 2-96-a 19.24 g (1.0 eq ), dibenzo [b, d] thiophene-2-Daily acid 6.46 g (1.1 eq), Pd (t-Bu 3 P) 2 0.13 g (0.01 eq) Dioxane, 10.93 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added, and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 16.59 g (yield 72%) of Compound 2-96. The mass spectrometry spectrum of the general formula (2-96) is shown in FIG. [M + H] &lt; / RTI &gt; = 896
합성예 18Synthesis Example 18
Figure PCTKR2018007083-appb-I000059
Figure PCTKR2018007083-appb-I000059
화학식 D 10.0 g (1.0 eq), 4-(4-(4-브로모페닐)-2-(피리딘-2-일)퀴나졸린-7-일)벤조니트릴 20.25 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 2-114-a 16.47 g (수율 65 %)을 얻었다. [M+H]=635Formula D 10.0 g (1.0 eq), 4- (4- (4- bromo-phenyl) -2- (pyridin-2-yl) quinazolin-7-yl) benzonitrile, 20.25 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq) of Pd (t-Bu 3 P) 2 and 0.05 g (0.002 eq) of Pd were dissolved in 250 ml of xylene and refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 16.47 g (yield 65%) of the compound 2-114-a. [M + H] &lt; + &gt; = 635
화학식 2-114-a 16.47 g (1.0 eq), (3-(디벤조[b,d]티오펜-2-일)페닐)보론산 8.69 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 11.03 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 2-114 13.98 g (수율 63 %)를 얻었다. [M+H]=8598.69 g (1.1 eq) of Pd (t-Bu 3 P), 16.47 g (1.0 eq) of the compound represented by the formula 2-114-a, 3- (dibenzo [b, d] thiophen- 2 (0.1 eq.) Was placed in 250 ml of dioxane, and 11.03 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 13.98 g (yield: 63%) of the compound 2-114. [M + H] &lt; + &gt; = 859
합성예 19Synthesis Example 19
Figure PCTKR2018007083-appb-I000060
Figure PCTKR2018007083-appb-I000060
화학식 B 10.0 g (1.0 eq), 1-클로로-4-(페닐-d5)프탈라진 10.74 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 3-2-a 12.41 g (수율 68 %)을 얻었다. [M+H]=462Formula B 10.0 g (1.0 eq), 1- chloro-4- (phenyl -d5) phthalazine 10.74 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq), Pd (t-Bu 3 P) 2 0.05 g (0.002 eq) was dissolved in 250 ml of xylene, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 12.41 g (yield: 68%) of the compound 3-2-a. [M + H] &lt; + &gt; = 462
화학식 3-2-a 12.41 g (1.0 eq), 디벤조[b,d]티오펜-2-일보론산 6.75 g (1.1 eq), Pd(t-Bu3P)2 0.14 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 11.42 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 3-2 11.09 g (수율 68 %)를 얻었다. [M+H]=610Formula 3-2-a 12.41 g (1.0 eq ), dibenzo [b, d] thiophene-2-Daily acid 6.75 g (1.1 eq), Pd (t-Bu 3 P) 2 0.14 g (0.01 eq) of (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added, and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 11.09 g (yield: 68%) of compound 3-2. [M + H] &lt; / RTI &gt; = 610
합성예 20Synthesis Example 20
Figure PCTKR2018007083-appb-I000061
Figure PCTKR2018007083-appb-I000061
화학식 I 10.0 g (1.0 eq), 1-클로로-4-(9,9-디페닐-9H-플루오렌-3-일)프탈라진 21.02 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 3-23-a 17.53 g (수율 63 %)을 얻었다. [M+H]=697Formula I 10.0 g (1.0 eq), 1- chloro-4- (9,9-diphenyl--9H- fluoren-3-yl) phthalazine 21.02 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq) and 0.05 g (0.002 eq) of Pd (t-Bu 3 P) 2 were dissolved in 250 ml of xylene, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 17.53 g (yield: 63%) of the compound 3-23-a. [M + H] = 697
화학식 3-23-a 17.53 g (1.0 eq), (4-(디벤조[b,d]퓨란-1-일)페닐)보론산 7.98 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.69 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 3-23 17.12 g (수율 75 %)를 얻었다. [M+H]=9057.98 g (1.1 eq) of Pd (t-Bu 3 P) 2 (1.0 eq), (4- (dibenzo [b, d] furan- put 0.13 g (0.01 eq) in 250ml of dioxane was stirred under reflux by placing a K 3 PO 4 10.69 g (2.0 eq) was dissolved in 80ml water. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 17.12 g (yield 75%) of Compound 3-23. [M + H] = 905
합성예 21Synthesis Example 21
Figure PCTKR2018007083-appb-I000062
Figure PCTKR2018007083-appb-I000062
화학식 H 10.0 g (1.0 eq), 1-클로로-4-(디벤조[b,d]퓨란-2-일)프탈라진 14.46 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 3-29-a 13.41 g (수율 62 %)을 얻었다. [M+H]=547Formula H 10.0 g (1.0 eq), 1- chloro-4- (dibenzo [b, d] furan-2-yl) phthalazine 14.46 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq), 0.05 g (0.002 eq) of Pd (t-Bu 3 P) 2 was dissolved in 250 ml of xylene, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 13.41 g (yield: 62%) of the compound 3-29-a. [M + H] &lt; + &gt; = 547
화학식 3-29-a 13.41 g (1.0 eq), 디벤조[b,d]티오펜-3-일보론산 6.16 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.43 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 3-29 11.74 g (수율 69 %)를 얻었다. [M+H]=695Formula for 3-29-a 13.41 g (1.0 eq ), dibenzo [b, d] thiophene-3 Daily acid 6.16 g (1.1 eq), Pd (t-Bu 3 P) 2 0.13 g (0.01 eq) Dioxane, and 10.43 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added, and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 11.74 g (yield 69%) of Compound 3-29. [M + H] = 695
합성예 22Synthesis Example 22
Figure PCTKR2018007083-appb-I000063
Figure PCTKR2018007083-appb-I000063
화학식 C 10.0 g (1.0 eq), 3-(4-클로로프탈라진-1-일)-9-페닐-9H-카바졸 17.74 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 3-37-a 15.57 g (수율 63 %)을 얻었다. [M+H]=62217.74 g (1.1 eq) of K 3 PO 4, 16.86 g (2.0 eq) of K 3 PO 4 , and 10.0 g (1.0 eq) of 3- (4- 0.05 g (0.002 eq) of Pd (t-Bu 3 P) 2 was dissolved in 250 ml of xylene, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 15.57 g (yield: 63%) of the compound 3-37-a. [M + H] &lt; / RTI &gt; = 622
화학식 3-37-a 15.57 g (1.0 eq), 디벤조[b,d]티오펜-1-일보론산 6.29 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.64 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 3-37 14.01 g (수율 73 %)를 얻었다. 화학식 3-37의 질량 분석 스펙트럼을 도 7에 나타내었다. [M+H]=770Formula for 3-37-a 15.57 g (1.0 eq ), dibenzo [b, d] thiophene-1-Daily acid 6.29 g (1.1 eq), Pd (t-Bu 3 P) 2 0.13 g (0.01 eq) Dioxane, and 10.64 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 14.01 g (yield: 73%) of compound 3-37. The mass spectrometry spectrum of Formula 3-37 is shown in FIG. [M + H] &lt; + &gt; = 770
합성예 23Synthesis Example 23
Figure PCTKR2018007083-appb-I000064
Figure PCTKR2018007083-appb-I000064
화학식 F 10.0 g (1.0 eq), 3-(4-클로로프탈라진-1-일)-11-페닐-11H-벤조[a]카바졸 19.93 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 3-45-a 16.74 g (수율 63 %)을 얻었다. [M+H]=67211.9 g (1.1 eq) of K 3 PO 4, 16.86 g of K 3 PO 4 (0.1 eq.), 10.0 g (1.0 eq) of 3- 2.0 eq) and 0.05 g (0.002 eq) of Pd (t-Bu 3 P) 2 were dissolved in 250 ml of xylene and refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 16.74 g (yield: 63%) of the compound 3-45-a. [M + H] = 672
화학식 3-45-a 16.74 g (1.0 eq), (4-(디벤조[b,d]퓨란-2-일)페닐)보론산 7.90 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.59 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 3-45 15.29 g (수율 70 %)를 얻었다. [M+H]=8807.90 g (1.1 eq) of Pd (t-Bu 3 P) 2 (0.45 g, 1.0 eq), (4- (dibenzo [b, 0.13 g (0.01 eq) of the compound was dissolved in 250 ml of dioxane, and 10.59 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added thereto, followed by reflux and stirring. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 15.29 g (yield 70%) of Compound 3-45. [M + H] &lt; + &gt; = 880
합성예 24Synthesis Example 24
Figure PCTKR2018007083-appb-I000065
Figure PCTKR2018007083-appb-I000065
화학식 E 10.0 g (1.0 eq), 4-클로로-1-(나프탈렌-2-일)-6-(페닐-d5)프탈라진 16.25 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 3-69-a 15.47 g (수율 66 %)을 얻었다. [M+H]=588Formula E 10.0 g (1.0 eq), 4- chloro-l- (naphthalen-2-yl) -6- (phenyl -d5) phthalazine 16.25 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq) And 0.05 g (0.002 eq) of Pd (t-Bu 3 P) 2 were dissolved in 250 ml of xylene, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 15.47 g (yield: 66%) of the compound 3-69-a. [M + H] = 588
화학식 3-69-a 15.47 g (1.0 eq), (4-(디벤조[b,d]티오펜-2-일)페닐)보론산 8.82 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 11.19 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 3-69 14.92 g (수율 70 %)를 얻었다. [M+H]=8128.82 g (1.1 eq) of Pd (t-Bu 3 P), 15.47 g (1.0 eq) of Formula 3-69-a, 4- (dibenzo [b, d] thiophen- 2 (0.1 eq.) Was placed in 250 ml of dioxane, and 11.19 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 14.92 g (yield 70%) of compound 3-69. [M + H] = 812
합성예 25Synthesis Example 25
Figure PCTKR2018007083-appb-I000066
Figure PCTKR2018007083-appb-I000066
화학식 D 10.0 g (1.0 eq), 1-(4-브로모나프탈렌-1-일)-4-(9,9-디메틸-9H-플루오렌-2-일)프탈라진 23.05 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 3-79-a 18.55 g (수율 67 %)을 얻었다. [M+H]=69923.05 g (1.1 eq) of 10.0 g (1.0 eq) of the compound of the formula D, 1- (4-bromonaphthalen-1-yl) -4- (9,9- 16.86 g (2.0 eq) of K 3 PO 4 and 0.05 g (0.002 eq) of Pd (t-Bu 3 P) 2 were dissolved in 250 ml of xylene and refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 18.55 g (yield 67%) of the compound 3-79-a. [M + H] = 699
화학식 3-79-a 18.55 g (1.0 eq), 디벤조[b,d]퓨란-2-일보론산 6.20 g (1.1 eq), Pd(t-Bu3P)2 0.14 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 11.28 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 3-79 14.07 g (수율 64 %)를 얻었다. [M+H]=831The compound of Formula 3-79-a 18.55 g (1.0 eq ), dibenzo [b, d] furan-2-Daily acid 6.20 g (1.1 eq), Pd (t-Bu 3 P) 2 0.14 g (0.01 eq) in dioxane , And 11.28 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added thereto, followed by refluxing and stirring. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 14.07 g (yield: 64%) of Compound 3-79. [M + H] &lt; + &gt; = 831
합성예 26Synthesis Example 26
Figure PCTKR2018007083-appb-I000067
Figure PCTKR2018007083-appb-I000067
화학식 A 10.0 g (1.0 eq), 6-([1,1'-비페닐]-3-일)-1-(4-브로모나프탈렌-1-일)-4-(디벤조[b,d]퓨란-3-일)프탈라진 28.56 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 3-90-a 20.15 g (수율 62 %)을 얻었다. [M+H]=8254-dibenzo [b, d (4-morpholin-3-yl) ] 250 for furan-3-yl) phthalazine 28.56 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq), Pd (t-Bu 3 P) 2 0.05 g (0.002 eq) and xylene (xylene) ml, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 20.15 g (yield: 62%) of the compound 3-90-a. [M + H] = 825
화학식 3-90-a 20.15 g (1.0 eq), (3-(디벤조[b,d]티오펜-4-일)페닐)보론산 8.18 g (1.1 eq), Pd(t-Bu3P)2 0.12 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.38 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 3-90 18.94 g (수율 74 %)를 얻었다. [M+H]=10498.18 g (1.1 eq) of Pd (t-Bu 3 P), 20.15 g (1.0 eq) of 3-90 dibenzoic acid, 3-8 dibenzo [b, d] thiophen- 2 was dissolved in 250 ml of dioxane, and 10.38 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added thereto, followed by reflux and stirring. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 18.94 g (yield: 74%) of Compound 3-90. [M + H] &lt; + &gt; = 1049
합성예 27Synthesis Example 27
Figure PCTKR2018007083-appb-I000068
Figure PCTKR2018007083-appb-I000068
화학식 G 10.0 g (1.0 eq), 2-(4-(4-브로모페닐)프탈라진-1-일)-9-(나프탈렌-2-일)-9H-카바졸 25.19 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 3-100-a 19.66 g (수율 66 %)을 얻었다. [M+H]=748(1.1 eq) of 10.0 g (1.0 eq) of the compound of formula (G) and 25.19 g of 2- (4- (4-bromophenyl) phthalazin- 16.86 g (2.0 eq) of K 3 PO 4 and 0.05 g (0.002 eq) of Pd (t-Bu 3 P) 2 were dissolved in 250 ml of xylene and refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 19.66 g (yield: 66%) of the compound 3-100-a. [M + H] &lt; + &gt; = 748
화학식 3-100-a 19.66 g (1.0 eq), (4-(디벤조[b,d]퓨란-3-일)페닐)보론산 8.34 g (1.1 eq), Pd(t-Bu3P)2 0.12 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 11.17 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 3-100 16.82 g (수율 67 %)를 얻었다. [M+H]=9568.34 g (1.1 eq) of Pd (t-Bu 3 P) 2 (1.0 eq), (4- (dibenzo [b, d] furan- 0.12 g (0.01 eq) of the compound was dissolved in 250 ml of dioxane, and 11.17 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added thereto, followed by reflux and stirring. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 16.82 g (yield 67%) of Compound 3-100. [M + H] = 956
합성예 28Synthesis Example 28
Figure PCTKR2018007083-appb-I000069
Figure PCTKR2018007083-appb-I000069
화학식 D 10.0 g (1.0 eq), 2-클로로-3-(4-(나프탈렌-2-일)페닐)퀴녹살린 16.03 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 4-15-a 15.03 g (수율 65 %)을 얻었다. [M+H]=583Formula D 10.0 g (1.0 eq), 2- chloro-3- (4- (naphthalen-2-yl) phenyl) quinoxaline 16.03 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq), Pd (t -Bu 3 P) 2 (0.05 g, 0.002 eq) was dissolved in 250 ml of xylene, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 15.03 g (yield: 65%) of the compound 4-15-a. [M + H] = 583
화학식 4-15-a 15.03 g (1.0 eq), (4-(디벤조[b,d]퓨란-3-일)페닐)보론산 8.18 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.96 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 4-15 12.25 g (수율 60 %)를 얻었다. [M+H]=7918.18 g (1.1 eq) of Pd (t-Bu 3 P) 2 (1.0 eq), 4- (dibenzo [b, d] furan- 0.13 g (0.01 eq) of dioxane was added to 250 ml of dioxane, and 10.96 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 12.25 g (yield: 60%) of the compound 4-15. [M + H] = 791
합성예 29Synthesis Example 29
Figure PCTKR2018007083-appb-I000070
Figure PCTKR2018007083-appb-I000070
화학식 I 10.0 g (1.0 eq), 2-(9,9'-스피로비[플루오렌]-3-일)-3-클로로퀴녹살린 20.93 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 4-26-a 17.93 g (수율 65 %)을 얻었다. [M+H]=695Formula I 10.0 g (1.0 eq), 2- (9,9'- RY lobby [fluorene; 3-yl) -3-chloro-quinoxaline 20.93 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq ) And 0.05 g (0.002 eq) of Pd (t-Bu 3 P) 2 were dissolved in 250 ml of xylene, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 17.93 g (yield: 65%) of the compound 4-26-a. [M + H] = 695
화학식 4-26-a 17.93 g (1.0 eq), 디벤조[b,d]퓨란-1-일보론산 6.02 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.96 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 4-26 15.33 g (수율 72 %)를 얻었다. [M+H]=827Formula 4-26-a 17.93 g (1.0 eq ), dibenzo [b, d] furan-1-Daily acid to 6.02 g (1.1 eq), Pd (t-Bu 3 P) 2 0.13 g (0.01 eq) in dioxane , And 10.96 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 15.33 g (yield 72%) of Compound 4-26. [M + H] &lt; + &gt; = 827
합성예 30Synthesis Example 30
Figure PCTKR2018007083-appb-I000071
Figure PCTKR2018007083-appb-I000071
화학식 B 10.0 g (1.0 eq), 8-(3-클로로퀴녹살린-2-일)-5-페닐-5H-벤조[b]카바졸 19.93 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 4-48-a 16.65 g (수율 62 %)을 얻었다. [M+H]=672Formula B 10.0 g (1.0 eq), 8- (3- chloro-quinoxalin-2-yl) -5-phenyl -5H- benzo [b] carbazol 19.93 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq) and 0.05 g (0.002 eq) of Pd (t-Bu 3 P) 2 were dissolved in 250 ml of xylene, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 16.65 g (yield: 62%) of the compound 4-48-a. [M + H] = 672
화학식 4-48-a 16.65 g (1.0 eq), 디벤조[b,d]퓨란-4-일보론산 5.79 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.53 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 4-48 13.74 g (수율 69 %)를 얻었다. [M+H]=804The compound of Formula 4-48-a 16.65 g (1.0 eq ), dibenzo [b, d] furan-4-Daily acid 5.79 g (1.1 eq), Pd (t-Bu 3 P) 2 0.13 g (0.01 eq) in dioxane , And 10.53 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added, and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 13.74 g (yield 69%) of compound 4-48. [M + H] &lt; + &gt; = 804
합성예 31Synthesis Example 31
Figure PCTKR2018007083-appb-I000072
Figure PCTKR2018007083-appb-I000072
화학식 F 10.0 g (1.0 eq), 2-클로로-3-(퀴놀린-7-일)퀴녹살린 12.75 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 4-57-a 14.25 g (수율 71 %)을 얻었다. [M+H]=508Formula F 10.0 g (1.0 eq), 2- chloro-3- (quinolin-7-yl) quinoxaline 12.75 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq), Pd (t-Bu 3 P) 2 0.05 g (0.002 eq) was dissolved in 250 ml of xylene, refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 14.25 g (yield 71%) of the compound 4-57-a. [M + H] &lt; / RTI &gt; = 508
화학식 4-57-a 14.25 g (1.0 eq), (4-(디벤조[b,d]퓨란-1-일)페닐)보론산 8.91 g (1.1 eq), Pd(t-Bu3P)2 0.14 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 11.93 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 4-57 12.62 g (수율 63 %)를 얻었다. 화학식 4-57의 질량 분석 스펙트럼을 도 8에 나타내었다. [M+H]=7168.91 g (1.1 eq) of Pd (t-Bu 3 P) 2 (4 eq.), 4- (dibenzo [b, d] furan- 0.14 g (0.01 eq) to put in 250ml dioxane was stirred under reflux by placing a K 3 PO 4 11.93 g (2.0 eq) was dissolved in 80ml water. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 12.62 g (yield: 63%) of Compound 4-57. The mass spectrometry spectrum of the formula 4-57 is shown in Fig. [M + H] &lt; + &gt; = 716
합성예 32Synthesis Example 32
Figure PCTKR2018007083-appb-I000073
Figure PCTKR2018007083-appb-I000073
화학식 C 10.0 g (1.0 eq), 2-([1,1'-비페닐]-3-일)-3-(6-브로모나프탈렌-2-일)퀴녹살린 21.30 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 4-64-a 17.47 g (수율 67 %)을 얻었다. [M+H]=65921.30 g (1.1 eq) of K, 10.0 g (1.0 eq) of the compound of formula C, 21.30 g (1.1 eq) of 2 - ([1,1'-biphenyl] -3- 3 PO 4 16.86 g (2.0 eq ), and the mixture was stirred under reflux melt Pd (t-Bu 3 P) 2 0.05 g (0.002 eq) in 250 ml of xylene (xylene). When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 17.47 g (yield: 67%) of the compound 4-64-a. [M + H] = 659
화학식 4-64-a 17.47 g (1.0 eq), (3-(디벤조[b,d]퓨란-3-일)페닐)보론산 8.41 g (1.1 eq), Pd(t-Bu3P)2 0.14 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 11.27 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 4-64 15.67 g (수율 68 %)를 얻었다. [M+H]=8678.41 g (1.1 eq) of Pd (t-Bu 3 P) 2 (1.0 eq), (3- (dibenzo [b, d] furan- put 0.14 g (0.01 eq) in 250ml of dioxane was stirred under reflux by placing a K 3 PO 4 11.27 g (2.0 eq) was dissolved in 80ml water. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 15.67 g (yield: 68%) of compound 4-64. [M + H] = 867
합성예 33Synthesis Example 33
Figure PCTKR2018007083-appb-I000074
Figure PCTKR2018007083-appb-I000074
화학식 H 10.0 g (1.0 eq), 2-(4-브로모나프탈렌-2-일)-6-페닐-3-(트리페닐렌-2-일)퀴녹살린 27.86 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 4-73-a 20.64 g (수율 64 %)을 얻었다. [M+H]=809Formula H 10.0 g (1.0 eq), 2- (4- bromo-2-yl) -6-phenyl-3- (triphenylene-2-yl) quinoxaline 27.86 g (1.1 eq) utilizing, K 3 PO 4 16.86 g (2.0 eq) of Pd (t-Bu 3 P) 2 and 0.05 g (0.002 eq) of Pd were dissolved in 250 ml of xylene and refluxed and stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 20.64 g (yield: 64%) of the compound 4-73-a. [M + H] &lt; + &gt; = 809
화학식 4-73-a 20.64 g (1.0 eq), (3-(디벤조[b,d]티오펜-2-일)페닐)보론산 8.54 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.84 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 4-73 17.49 g (수율 66 %)를 얻었다. [M+H]=10338.54 g (1.1 eq) of Pd (t-Bu 3 P), 20.44 g (1.0 eq) of formula 4-73-a, 8.54 g (1.1 eq) of (3- (dibenzo [b, d] thiophen- 2 was dissolved in 250 ml of dioxane, and 10.84 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added, and the mixture was refluxed and stirred. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 17.49 g (yield 66%) of compound 4-73. [M + H] &lt; + &gt; = 1033
합성예 34Synthesis Example 34
Figure PCTKR2018007083-appb-I000075
Figure PCTKR2018007083-appb-I000075
화학식 A 10.0 g (1.0 eq), 3-(4-브로모페닐)-2-(9,9-디메틸-9H-플루오렌-3-일)-6-(페난트렌-9-일)퀴녹살린 28.56 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 4-80-a 21.61 g (수율 66 %)을 얻었다. [M+H]=8259-dimethyl-9H-fluoren-3-yl) -6- (phenanthrene-9-yl) quinoxaline 28.56 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq), and the mixture was stirred under reflux melt Pd (t-Bu 3 P) 2 0.05 g (0.002 eq) in 250 ml of xylene (xylene). When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 21.61 g (yield: 66%) of the compound 4-80-a. [M + H] = 825
화학식 4-80-a 21.61 g (1.0 eq), 디벤조[b,d]티오펜-4-일보론산 6.58 g (1.1 eq), Pd(t-Bu3P)2 0.13 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 11.13 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 4-80 18.10 g (수율 71 %)를 얻었다. [M+H]=973Formula for 4-80-a 21.61 g (1.0 eq ), dibenzo [b, d] thiophene-4 Daily acid 6.58 g (1.1 eq), Pd (t-Bu 3 P) 2 0.13 g (0.01 eq) placed in 250ml of dioxane it was stirred under reflux by placing a K 3 PO 4 11.13 g (2.0 eq) was dissolved in 80ml water. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 18.10 g (yield: 71%) of compound 4-80. [M + H] &lt; + &gt; = 973
합성예 35Synthesis Example 35
Figure PCTKR2018007083-appb-I000076
Figure PCTKR2018007083-appb-I000076
화학식 J 10.0 g (1.0 eq), 9-([1,1'-비페닐]-4-일)-3-(3-클로로-6-(피리딘-4-일)퀴녹살린-2-일)-9H-카바졸 24.43 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 4-99-a 17.92 g (수율 58 %)을 얻었다. [M+H]=7754-yl) -3- (3-chloro-6- (pyridin-4-yl) quinoxalin-2-yl) -9H- carbazol 24.43 g (1.1 eq), K 3 PO 4 16.86 g (2.0 eq), is refluxed for dissolving Pd (t-Bu 3 P) 2 0.05 g (0.002 eq) in 250 ml of xylene (xylene) Lt; / RTI &gt; When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 17.92 g (yield: 58%) of the compound 4-99-a. [M + H] = 775
화학식 4-99-a 17.92 g (1.0 eq), (4-(디벤조[b,d]티오펜-4-일)페닐)보론산 7.74 g (1.1 eq), Pd(t-Bu3P)2 0.12 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 9.82 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 4-99 15.36 g (수율 66 %)를 얻었다. [M+H]=999, 7.74 g (1.1 eq) of Pd (t-Bu 3 P), 17.92 g (1.0 eq) of 4-99 dibenzo [b, d] thiophen- 2 was dissolved in 250 ml of dioxane, and 9.82 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added thereto, followed by reflux and stirring. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 15.36 g (yield 66%) of compound 4-99. [M + H] = 999
합성예 36Synthesis Example 36
Figure PCTKR2018007083-appb-I000077
Figure PCTKR2018007083-appb-I000077
화학식 E 10.0 g (1.0 eq), 3-(6,7-디([1,1'-비페닐]-2-일)-3-클로로퀴녹살린-2-일)-7-페닐-7H-벤조[c]카바졸 33.23 g (1.1 eq), K3PO4 16.86 g (2.0 eq), Pd(t-Bu3P)2 0.05 g (0.002 eq)를 자일렌(Xylene) 250 ml 에 녹여 환류하여 교반했다. 3 시간 후 반응이 종료되면 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 4-113-a 23.64 g (수율 61 %)을 얻었다. [M+H]=976(10 eq.) Of the compound of formula (E), 1.0 g (1.0 eq) of 3- (6,7-di [(1,1'-biphenyl- A solution of 33.23 g (1.1 eq) of benzo [c] carbazole, 16.86 g (2.0 eq) of K 3 PO 4 and 0.05 g (0.002 eq) of Pd (t- Bu 3 P) 2 was dissolved in 250 ml of xylene, And stirred. When the reaction was completed after 3 hours, the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 23.64 g (yield: 61%) of the compound 4-113-a. [M + H] &lt; + &gt; = 976
화학식 4-113-a 23.64 g (1.0 eq), (4-(디벤조[b,d]티오펜-2-일)페닐)보론산 8.11 g (1.1 eq), Pd(t-Bu3P)2 0.12 g (0.01 eq) 를 다이옥산 250ml에 넣고 물 80ml에 녹인 K3PO4 10.23 g (2.0 eq)를 넣어서 환류하여 교반했다. 2 시간 후 반응이 종료되면 염이 녹아 있는 물층을 제거하고 감압하여 용매를 제거했다. 이 후 클로로포름에 완전히 녹여 물로 씻어주고 다시 감압하여 용매를 50% 정도 제거했다. 다시 환류 상태에서 에틸아세테이트를 넣어주며 결정을 떨어트려 식힌 후 여과했다. 이를 컬럼크로마토그래피하여 화합물 4-113 18.09 g (수율 62 %)를 얻었다. [M+H]=12008.11 g (1.1 eq) of Pd (t-Bu 3 P), 8.11 g (1.0 eq) of 4- (dibenzo [b, d] thiophen- 2 was dissolved in 250 ml of dioxane, and 10.23 g (2.0 eq) of K 3 PO 4 dissolved in 80 ml of water was added thereto, followed by reflux and stirring. After the reaction was completed after 2 hours, the water layer containing the salt was removed, and the solvent was removed by decompression. After that, it was completely dissolved in chloroform, washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 18.09 g (yield 62%) of the compound 4-113. [M + H] = 1200
<실험예><Experimental Example>
비교예 1Comparative Example 1
ITO(indium tin oxide)가 1,000Å의 두께로 박막 코팅된 유리 기판을 세제를 녹인 증류수에 넣고 초음파로 세척하였다. 이때, 세제로는 피셔사(Fischer Co.) 제품을 사용하였으며, 증류수로는 밀러포어사(Millipore Co.) 제품의 필터(Filter)로 2차로 걸러진 증류수를 사용하였다. ITO를 30분간 세척한 후 증류수로 2회 반복하여 초음파 세척을 10분간 진행하였다. 증류수 세척이 끝난 후, 이소프로필알콜, 아세톤, 메탄올의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 수송시켰다. 또한, 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후 진공 증착기로 기판을 수송시켰다.The glass substrate coated with ITO (indium tin oxide) thin film with a thickness of 1,000 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, Fischer Co. product was used as a detergent, and distilled water, which was secondly filtered with a filter of Millipore Co., was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.
이렇게 준비된 ITO 투명 전극 위에 정공주입층으로 하기 HI-1 화합물을 1150Å의 두께로 형성하되 하기 A-1 화합물을 1.5% 농도로 p-도핑 하였다. 상기 정공주입층 위에 하기 HT-1 화합물을 진공 증착하여 막 두께 800Å 의 정공수송층을 형성하였다. 이어서, 상기 정공수송층 위에 막 두께 150Å으로 하기 EB-1 화합물을 진공 증착하여 전자저지층을 형성하였다. 이어서, 상기 EB-1 증착막 위에 하기 RH-1 화합물과 하기 Dp-39 화합물을 98:2의 중량비로 진공 증착하여 400Å 두께의 적색 발광층을 형성하였다. 상기 발광층 위에 막 두께 30Å으로 하기 HB-1 화합물을 진공 증착하여 정공저지층을 형성하였다. 이어서, 상기 정공저지층 위에 하기 ET-1 화합물과 하기 LiQ 화합물을 2:1의 중량비로 진공 증착하여 300Å의 두께로 전자 주입 및 수송층을 형성하였다. 상기 전자 주입 및 수송층 위에 순차적으로 12Å 두께로 리튬플로라이드(LiF)와 1,000Å 두께로 알루미늄을 증착하여 음극을 형성하였다. The following HI-1 compound was formed to a thickness of 1150 ANGSTROM as a hole injecting layer on the ITO transparent electrode thus prepared, and the following compound A-1 was p-doped at a concentration of 1.5%. The following HT-1 compound was vacuum deposited on the hole injection layer to form a hole transport layer having a thickness of 800 ANGSTROM. Subsequently, EB-1 compound having a thickness of 150 ANGSTROM was vacuum-deposited on the hole transport layer to form an electron blocking layer. Subsequently, the following RH-1 compound and the following Dp-39 compound were vapor-deposited on the EB-1 vapor-deposited film at a weight ratio of 98: 2 to form a 400Å thick red light emitting layer. HB-1 compound was vacuum deposited on the light emitting layer to a film thickness of 30 ANGSTROM to form a hole blocking layer. Subsequently, the following ET-1 compound and the following LiQ compound were vacuum-deposited on the hole blocking layer at a weight ratio of 2: 1 to form an electron injecting and transporting layer having a thickness of 300 Å. Lithium fluoride (LiF) and aluminum having a thickness of 1,000 Å were sequentially deposited on the electron injecting and transporting layer to form a cathode.
상기의 과정에서 유기물의 증착속도는 0.4~0.7Å/sec를 유지하였고, 음극의 리튬플로라이드는 0.3Å/sec, 알루미늄은 2Å/sec의 증착 속도를 유지하였으며, 증착시 진공도는 2×10-7 ~ 5×10-6 torr를 유지하여, 유기 전계 발광 소자를 제작하였다.Was maintained at the deposition rate was 0.4 ~ 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was 0.3Å / sec, aluminum is deposited at a rate of 2Å / sec, During the deposition, a vacuum 2 × 10 - 7 to 5 x 10 &lt; -6 &gt; torr. Thus, an organic electroluminescent device was fabricated.
Figure PCTKR2018007083-appb-I000078
Figure PCTKR2018007083-appb-I000078
실시예 1 내지 실시예 36Examples 1 to 36
비교예 1의 유기 전계 발광 소자에서 RH-1 대신 하기 표 1에 기재된 화합물을 사용하는 것을 제외하고는, 상기 비교예 1과 동일한 방법으로 유기 전계 발광 소자를 제조하였다. An organic electroluminescent device was produced in the same manner as in Comparative Example 1, except that the compound shown in the following Table 1 was used in place of RH-1 in the organic electroluminescent device of Comparative Example 1.
비교예 2 내지 비교예 10Comparative Examples 2 to 10
비교예 1의 유기 전계 발광 소자에서 RH-1 대신 하기 표 1에 기재된 화합물을 사용하는 것을 제외하고는, 상기 비교예 1과 동일한 방법으로 유기 전계 발광 소자를 제조하였다. An organic electroluminescent device was produced in the same manner as in Comparative Example 1, except that the compound shown in the following Table 1 was used in place of RH-1 in the organic electroluminescent device of Comparative Example 1.
Figure PCTKR2018007083-appb-I000079
Figure PCTKR2018007083-appb-I000079
상기 실시예 1 내지 실시예 36, 비교예 1 내지 비교예 10에서 제조한 유기 전계 발광 소자에 전류를 인가하였을 때, 전압, 효율, 수명을 측정하고 그 결과를 하기 표 1에 나타내었다. T95는 휘도가 초기 휘도(5000 nit)에서 95%로 감소되는데 소요되는 시간을 의미한다.The voltage, efficiency and lifetime of the organic electroluminescent device fabricated in Examples 1 to 36 and Comparative Examples 1 to 10 were measured, and the results are shown in Table 1 below. T95 means the time required for the luminance to decrease from the initial luminance (5000 nits) to 95%.
구분division 물질matter 구동전압(V)The driving voltage (V) 효율(cd/A)Efficiency (cd / A) 수명 T95(hr)Life T95 (hr) 발광색Luminous color
비교예 1Comparative Example 1 RH-1RH-1 4.664.66 30.230.2 160160 적색Red
실시예 1Example 1 화합물 1-9Compound 1-9 4.234.23 42.842.8 318318 적색Red
실시예 2Example 2 화합물 1-16Compound 1-16 4.374.37 39.739.7 329329 적색Red
실시예 3Example 3 화합물 1-30Compound 1-30 4.294.29 42.842.8 253253 적색Red
실시예 4Example 4 화합물 1-44Compound 1-44 4.514.51 46.546.5 198198 적색Red
실시예 5Example 5 화합물 1-59Compound 1-59 4.164.16 45.845.8 248248 적색Red
실시예 6Example 6 화합물 1-68Compound 1-68 4.384.38 40.940.9 273273 적색Red
실시예 7Example 7 화합물 1-89Compound 1-89 4.174.17 42.142.1 329329 적색Red
실시예 8Example 8 화합물 1-95Compound 1-95 4.524.52 40.740.7 347347 적색Red
실시예 9Example 9 화합물 1-107Compound 1-107 4.294.29 42.742.7 291291 적색Red
실시예 10Example 10 화합물 2-7Compound 2-7 4.434.43 41.741.7 306306 적색Red
실시예 11Example 11 화합물 2-21Compound 2-21 4.294.29 43.143.1 314314 적색Red
실시예 12Example 12 화합물 2-28Compound 2-28 4.314.31 44.844.8 276276 적색Red
실시예 13Example 13 화합물 2-53Compound 2-53 4.184.18 42.742.7 294294 적색Red
실시예 14Example 14 화합물 2-64Compound 2-64 4.454.45 43.143.1 287287 적색Red
실시예 15Example 15 화합물 2-76Compound 2-76 4.234.23 44.844.8 267267 적색Red
실시예 16Example 16 화합물 2-79Compound 2-79 4.184.18 41.741.7 294294 적색Red
실시예 17Example 17 화합물 2-96Compound 2-96 4.254.25 43.143.1 283283 적색Red
실시예 18Example 18 화합물 2-114Compound 2-114 4.194.19 42.542.5 296296 적색Red
실시예 19Example 19 화합물 3-2Compound 3-2 4.334.33 41.741.7 342342 적색Red
실시예 20Example 20 화합물 3-23Compound 3-23 4.234.23 40.940.9 323323 적색Red
실시예 21Example 21 화합물 3-29Compound 3-29 4.414.41 43.143.1 298298 적색Red
실시예 22Example 22 화합물 3-37Compound 3-37 4.194.19 40.940.9 329329 적색Red
실시예 23Example 23 화합물 3-45Compound 3-45 4.324.32 41.541.5 319319 적색Red
실시예 24Example 24 화합물 3-69Compound 3-69 4.254.25 43.943.9 295295 적색Red
실시예 25Example 25 화합물 3-79Compound 3-79 4.044.04 44.244.2 281281 적색Red
실시예 26Example 26 화합물 3-90Compound 3-90 4.184.18 43.543.5 279279 적색Red
실시예 27Example 27 화합물 3-100Compound 3-100 4.354.35 41.841.8 335335 적색Red
실시예 28Example 28 화합물 4-15Compounds 4-15 4.274.27 43.843.8 302302 적색Red
실시예 29Example 29 화합물 4-26Compound 4-26 4.124.12 41.241.2 325325 적색Red
실시예 30Example 30 화합물 4-48Compound 4-48 4.504.50 42.542.5 284284 적색Red
실시예 31Example 31 화합물 4-57Compound 4-57 4.314.31 38.938.9 302302 적색Red
실시예 32Example 32 화합물 4-64Compound 4-64 4.284.28 39.839.8 289289 적색Red
실시예 33Example 33 화합물 4-73Compound 4-73 4.424.42 40.840.8 233233 적색Red
실시예 34Example 34 화합물 4-80Compound 4-80 4.394.39 36.836.8 201201 적색Red
실시예 35Example 35 화합물 4-99Compound 4-99 4.374.37 37.237.2 171171 적색Red
실시예 36Example 36 화합물 4-113Compound 4-113 4.214.21 36.836.8 187187 적색Red
비교예 2Comparative Example 2 RH-2RH-2 4.684.68 31.031.0 163163 적색Red
비교예 3Comparative Example 3 RH-3RH-3 4.344.34 33.633.6 173173 적색Red
비교예 4Comparative Example 4 RH-4RH-4 4.584.58 37.137.1 121121 적색Red
비교예 5Comparative Example 5 RH-5RH-5 4.434.43 30.630.6 106106 적색Red
비교예 6Comparative Example 6 RH-6RH-6 4.624.62 32.932.9 154154 적색Red
비교예 7Comparative Example 7 RH-7RH-7 4.424.42 36.736.7 140140 적색Red
비교예 8Comparative Example 8 RH-8RH-8 4.494.49 34.034.0 147147 적색Red
비교예 9Comparative Example 9 RH-9RH-9 4.354.35 37.337.3 126126 적색Red
비교예 10Comparative Example 10 RH-10RH-10 4.814.81 32.832.8 8181 적색Red
상기 표 1의 결과로부터, 실험예 1 내지 36과 비교예 1 내지 5, 7 내지 8, 및 10을 비교하면, 상기 화학식 1의 Ar1이 2환의 헤테로고리인 화합물은 Ar1이 N포함 단환의 헤테로고리, N포함 3환 또는 4환의 헤테로고리인 화합물에 비하여 유기 전계 발광 소자에서 구동전압, 효율 및 수명면에서 우수한 특성을 나타내는 것을 확인할 수 있었다. From the results shown in Table 1, it can be seen from the results of Experimental Examples 1 to 36 and Comparative Examples 1 to 5, 7 to 8, and 10 that Ar1 in the formula 1 is a dicyclic heterocycle, Ar1 is a monocyclic hetero ring containing N , And N, which is a triple or quadruple heterocyclic ring, exhibits excellent characteristics in terms of driving voltage, efficiency, and lifetime in an organic electroluminescent device.
또한, 실험예 1 내지 36과 비교예 6을 비교하면, 상기 화학식 1의 벤조[b]카바졸인 화합물은 벤조[a]카바졸인 화합물에 비하여 유기 전계 발광 소자에서 구동전압, 효율 및 수명면에서 우수한 특성을 나타내는 것을 확인할 수 있었다.Comparing the examples 1 to 36 and the comparative example 6, it is found that the compound having the benzo [b] carbazole of the formula 1 is superior in the driving voltage, efficiency and lifetime in the organic electroluminescent device as compared with the benzo [a] , Respectively.
실험예 1 내지 36과 비교예 9를 비교하면, Ar1이 디벤조티오펜인 화합물에 비하여 본 발명의 화합물이 유기 전계 발광 소자에서 구동전압, 효율 및 수명면에서 우수한 특성을 나타내는 것을 확인할 수 있었다Comparing Experimental Examples 1 to 36 and Comparative Example 9, it was confirmed that the compound of the present invention exhibited excellent characteristics in terms of driving voltage, efficiency and lifetime in comparison with the compound in which Ar1 is dibenzothiophene
또한, 실험예 1 내지 36과 비교예 10을 비교하면, 본원 발명의 화합물은 Ar1이 N포함 단환의 헤테로고리이고, X가 C인 화합물과 비교하여 유기 전계 발광 소자에서 구동전압, 효율에서 우수한 특성을 갖으며, 특히 수명면에서 보다 우수한 특성을 갖는 것을 확인할 수 있었다. Comparing Experimental Examples 1 to 36 and Comparative Example 10, the compound of the present invention is superior in driving voltage and efficiency in an organic electroluminescent device as compared with a compound in which Ar1 is a monocyclic hetero ring containing N and X is C , And it was confirmed that it has superior characteristics particularly in terms of life span.

Claims (12)

  1. 하기 화학식 1로 표시되는 화합물:A compound represented by the following formula (1):
    [화학식 1][Chemical Formula 1]
    Figure PCTKR2018007083-appb-I000080
    Figure PCTKR2018007083-appb-I000080
    상기 화학식 1에 있어서, In Formula 1,
    Ar1은 N을 포함하는 2환의 치환 또는 비치환된 헤테로고리기이고, Ar 1 is a divalent substituted or unsubstituted heterocyclic group containing N,
    X는 O 또는 S이고, X is O or S,
    L1 및 L2는 서로 같거나 상이하고, 각각 독립적으로 직접결합, 치환 또는 비치환된 아릴렌기, 또는 치환 또는 비치환된 2가의 헤테로고리기이며,L 1 and L 2 are the same or different from each other and are each independently a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted divalent heterocyclic group,
    R1 내지 R4는 서로 같거나 상이하고, 각각 독립적으로 수소, 중수소, 할로겐기, 시아노기, 치환 또는 비치환된 알킬기, 치환 또는 비치환된 알콕시기, 치환 또는 비치환된 아릴기, 또는 치환 또는 비치환된 헤테로고리기이고, R 1 to R 4 are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, A substituted or unsubstituted heterocyclic group,
    n은 0 내지 4의 정수이며, n이 2 이상인 경우 R1은 서로 같거나 상이하고,n is an integer of 0 to 4, and when n is 2 or more, R1 is the same or different from each other,
    m은 0 내지 6의 정수이고, m이 2 이상인 경우 R2는 서로 같거나 상이하고,m is an integer of 0 to 6, and when m is 2 or more, R2 is the same or different,
    o는 0 내지 3의 정수이고, o가 2 이상인 경우 R3는 서로 같거나 상이하고, o is an integer of 0 to 3, and when o is 2 or more, R3 is the same or different from each other,
    p는 0 내지 4의 정수이고, p가 2 이상인 경우 R4는 서로 같거나 상이하고, p is an integer of 0 to 4, and when p is 2 or more, R4 is the same or different from each other,
    0≤n+m≤9이다.0? N + m? 9.
  2. 청구항 1에 있어서, 상기 Ar1은 치환 또는 비치환된 퀴나졸린기; 치환 또는 비치환된 프탈라진기; 또는 치환 또는 비치환된 퀴녹살린기인 것인 화합물.[2] The compound according to claim 1, wherein Ar &lt; 1 &gt; is a substituted or unsubstituted quinazoline group; A substituted or unsubstituted phthalazine group; Or a substituted or unsubstituted quinoxaline group.
  3. 청구항 1에 있어서, 상기 Ar1은 하기 화학식 2 내지 5 중 어느 하나로 표시되는 것인 화합물:The compound according to claim 1, wherein Ar1 is represented by any one of the following formulas (2) to (5):
    [화학식 2](2)
    Figure PCTKR2018007083-appb-I000081
    Figure PCTKR2018007083-appb-I000081
    [화학식 3](3)
    Figure PCTKR2018007083-appb-I000082
    Figure PCTKR2018007083-appb-I000082
    [화학식 4][Chemical Formula 4]
    Figure PCTKR2018007083-appb-I000083
    Figure PCTKR2018007083-appb-I000083
    [화학식 5][Chemical Formula 5]
    Figure PCTKR2018007083-appb-I000084
    Figure PCTKR2018007083-appb-I000084
    상기 화학식 2 내지 5에 있어서, In the above formulas 2 to 5,
    Figure PCTKR2018007083-appb-I000085
    은 상기 화학식 1의 L1과 결합하는 위치를 의미하고,
    Figure PCTKR2018007083-appb-I000085
    Refers to a position at which L &lt; 1 &gt; in formula (1)
    R21 내지 R25, R31 내지 R35, R41 내지 R45, 및 R51 내지 R55는 서로 같거나 상이하고, 서로 독립적으로 수소; 중수소; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다. R21 to R25, R31 to R35, R41 to R45, and R51 to R55 are the same or different and independently of one another are hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  4. 청구항 1에 있어서, 상기 R3 및 R4는 수소인 것인 화합물.2. The compound according to claim 1, wherein R3 and R4 are hydrogen.
  5. 청구항 1에 있어서, 상기 L1은 직접결합; 페닐렌기; 또는 나프틸렌기인 것인 화합물.[2] The compound according to claim 1, wherein L1 is a direct bond; A phenylene group; Or a naphthylene group.
  6. 청구항 1에 있어서, 상기 L2은 직접결합 또는 페닐렌기인 것인 화합물.2. The compound according to claim 1, wherein L2 is a direct bond or a phenylene group.
  7. 청구항 1에 있어서, 상기 R1 및 R2는 수소인 것인 화합물.2. The compound of claim 1, wherein R1 and R2 are hydrogen.
  8. 청구항 1에 있어서, 상기 화학식 1의 화합물은 하기 구조식들 중에서 선택되어지는 것인 화합물:The compound of claim 1, wherein the compound of formula (1) is selected from the following formulas:
    Figure PCTKR2018007083-appb-I000086
    Figure PCTKR2018007083-appb-I000086
    Figure PCTKR2018007083-appb-I000087
    Figure PCTKR2018007083-appb-I000087
    Figure PCTKR2018007083-appb-I000088
    Figure PCTKR2018007083-appb-I000088
    Figure PCTKR2018007083-appb-I000089
    Figure PCTKR2018007083-appb-I000089
    Figure PCTKR2018007083-appb-I000090
    Figure PCTKR2018007083-appb-I000090
    Figure PCTKR2018007083-appb-I000091
    Figure PCTKR2018007083-appb-I000091
    Figure PCTKR2018007083-appb-I000092
    Figure PCTKR2018007083-appb-I000092
    Figure PCTKR2018007083-appb-I000093
    Figure PCTKR2018007083-appb-I000093
    Figure PCTKR2018007083-appb-I000094
    Figure PCTKR2018007083-appb-I000094
    Figure PCTKR2018007083-appb-I000095
    Figure PCTKR2018007083-appb-I000095
    Figure PCTKR2018007083-appb-I000096
    Figure PCTKR2018007083-appb-I000096
    Figure PCTKR2018007083-appb-I000097
    Figure PCTKR2018007083-appb-I000097
    Figure PCTKR2018007083-appb-I000098
    Figure PCTKR2018007083-appb-I000098
    Figure PCTKR2018007083-appb-I000099
    Figure PCTKR2018007083-appb-I000099
    Figure PCTKR2018007083-appb-I000100
    Figure PCTKR2018007083-appb-I000100
    Figure PCTKR2018007083-appb-I000101
    Figure PCTKR2018007083-appb-I000101
  9. 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자로서, 상기 유기물층 중 1층 이상은 청구항 1 내지 8 중 어느 한 항에 따른 화합물을 포함하는 것인 유기 전계 발광 소자.A first electrode; A second electrode facing the first electrode; And at least one organic compound layer provided between the first electrode and the second electrode, wherein at least one of the organic compound layers comprises a compound according to any one of claims 1 to 8 Organic electroluminescent device.
  10. 청구항 9에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화합물을 포함하는 것인 유기 전계 발광 소자.The organic electroluminescent device according to claim 9, wherein the organic layer includes a light emitting layer, and the light emitting layer comprises the compound.
  11. 청구항 9에 있어서, 상기 유기물층은 전자주입층, 전자수송층, 또는 전자 주입 및 수송층을 포함하고, 상기 전자주입층, 전자수송층, 또는 전자 주입 및 수송층은 상기 화합물을 포함하는 것인 유기 전계 발광 소자.The organic electroluminescent device according to claim 9, wherein the organic material layer includes an electron injection layer, an electron transport layer, or an electron injection and transport layer, and the electron injection layer, the electron transport layer, or the electron injection and transport layer comprises the compound.
  12. 청구항 9에 있어서, 상기 유기물층은 정공주입층, 정공수송층, 또는 정공 주입 및 수송층을 포함하고, 상기 정공주입층, 정공수송층, 또는 정공 주입 및 수송층은 상기 화합물을 포함하는 것인 유기 전계 발광 소자.[12] The organic electroluminescent device according to claim 9, wherein the organic compound layer includes a hole injection layer, a hole transport layer, or a hole injection and transport layer, and the hole injection layer, the hole transport layer, or the hole injection and transport layer comprises the compound.
PCT/KR2018/007083 2017-06-23 2018-06-22 Compound and organic electroluminescent device comprising same WO2018236182A1 (en)

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